WO2015115589A1 - Halogen atom-substituted polymerizable compound - Google Patents
Halogen atom-substituted polymerizable compound Download PDFInfo
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- WO2015115589A1 WO2015115589A1 PCT/JP2015/052639 JP2015052639W WO2015115589A1 WO 2015115589 A1 WO2015115589 A1 WO 2015115589A1 JP 2015052639 W JP2015052639 W JP 2015052639W WO 2015115589 A1 WO2015115589 A1 WO 2015115589A1
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- liquid crystal
- ppm
- aligning agent
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- 0 CC(*)=CC(C(C1=*=C11)=CC=C1O)=CC=C(C=C*)C(C(C1=*=C)=*)=CC=C1O Chemical compound CC(*)=CC(C(C1=*=C11)=CC=C1O)=CC=C(C=C*)C(C(C1=*=C)=*)=CC=C1O 0.000 description 3
- DQOOWXOFTUMWDJ-UHFFFAOYSA-N C=C(CC(COc(cc1)ccc1-c(cc1)cc(F)c1OCC(CC1=C)OC1=O)O1)C1=O Chemical compound C=C(CC(COc(cc1)ccc1-c(cc1)cc(F)c1OCC(CC1=C)OC1=O)O1)C1=O DQOOWXOFTUMWDJ-UHFFFAOYSA-N 0.000 description 2
- MQQBQJQHUARDQC-UHFFFAOYSA-N C=C(CC(CCCCOc(cc1)ccc1-c(cc1)cc(F)c1OCCCCC(CC1=C)OC1=O)O1)C1=O Chemical compound C=C(CC(CCCCOc(cc1)ccc1-c(cc1)cc(F)c1OCCCCC(CC1=C)OC1=O)O1)C1=O MQQBQJQHUARDQC-UHFFFAOYSA-N 0.000 description 1
- ITIFTJPISDIQEV-UHFFFAOYSA-N C=C(CC(CCCCOc(cc1)ccc1-c1ccc(-c(cc2)ccc2OCCCCC(CC2=C)OC2=O)c(F)c1)O1)C1=O Chemical compound C=C(CC(CCCCOc(cc1)ccc1-c1ccc(-c(cc2)ccc2OCCCCC(CC2=C)OC2=O)c(F)c1)O1)C1=O ITIFTJPISDIQEV-UHFFFAOYSA-N 0.000 description 1
- XUMXEBVXTJJYNW-UHFFFAOYSA-N C=C(CC(CCCOc(cc1)ccc1-c(cc1)cc(F)c1OCCCC(CC1=C)OC1=O)O1)C1=O Chemical compound C=C(CC(CCCOc(cc1)ccc1-c(cc1)cc(F)c1OCCCC(CC1=C)OC1=O)O1)C1=O XUMXEBVXTJJYNW-UHFFFAOYSA-N 0.000 description 1
- WLDXOXZCSJEXTB-UHFFFAOYSA-N C=C(CC(CCOc(cc1)ccc1-c(cc1)cc(F)c1OCCC(CC1=C)OC1=O)O1)C1=O Chemical compound C=C(CC(CCOc(cc1)ccc1-c(cc1)cc(F)c1OCCC(CC1=C)OC1=O)O1)C1=O WLDXOXZCSJEXTB-UHFFFAOYSA-N 0.000 description 1
- XEKSFJWUQIYBRV-UHFFFAOYSA-N C=C(CC(COc(cc1)ccc1-c(cc1)cc(F)c1-c(cc1)ccc1OCC(CC1=C)OC1=O)O1)C1=O Chemical compound C=C(CC(COc(cc1)ccc1-c(cc1)cc(F)c1-c(cc1)ccc1OCC(CC1=C)OC1=O)O1)C1=O XEKSFJWUQIYBRV-UHFFFAOYSA-N 0.000 description 1
- XSCNFWBZYPIMEG-UHFFFAOYSA-N CC(C)(C(C(C=C1)=CCC1OO)=O)O Chemical compound CC(C)(C(C(C=C1)=CCC1OO)=O)O XSCNFWBZYPIMEG-UHFFFAOYSA-N 0.000 description 1
- ZALUIMCQRLGTIY-UHFFFAOYSA-N CC(C)(C(c(cc1)ccc1OCCOc(c([N+]([O-])=O)c1)ccc1[N+]([O-])=O)=O)O Chemical compound CC(C)(C(c(cc1)ccc1OCCOc(c([N+]([O-])=O)c1)ccc1[N+]([O-])=O)=O)O ZALUIMCQRLGTIY-UHFFFAOYSA-N 0.000 description 1
- RLJDULFUDRUNJF-UHFFFAOYSA-N CC(C)(Cc(cc1)ccc1OCCOc(ccc(N)c1)c1N)O Chemical compound CC(C)(Cc(cc1)ccc1OCCOc(ccc(N)c1)c1N)O RLJDULFUDRUNJF-UHFFFAOYSA-N 0.000 description 1
- LOTKRQAVGJMPNV-UHFFFAOYSA-N [O-][N+](c(cc1[N+]([O-])=O)ccc1F)=O Chemical compound [O-][N+](c(cc1[N+]([O-])=O)ccc1F)=O LOTKRQAVGJMPNV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/58—One oxygen atom, e.g. butenolide
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
Definitions
- the present invention relates to a polymerizable compound substituted with a halogen atom, a liquid crystal aligning agent containing the polymerizable compound substituted with a halogen atom, a liquid crystal alignment film, and a liquid crystal display element.
- a liquid crystal display element of a method in which liquid crystal molecules aligned perpendicular to a substrate are responded by an electric field also referred to as a vertical alignment (VA) method
- an ultraviolet ray is applied while applying a voltage to the liquid crystal molecules in the manufacturing process.
- a photopolymerizable compound is added to a liquid crystal composition in advance and used together with a vertical alignment film such as polyimide to irradiate ultraviolet rays while applying a voltage to a liquid crystal cell.
- a technique for increasing the response speed of liquid crystal for example, see Patent Document 1 and Non-Patent Document 1) is known (PSA (Polymer sustained Alignment) type liquid crystal display).
- the direction in which the liquid crystal molecules tilt in response to an electric field is controlled by protrusions provided on the substrate or slits provided on the display electrode, but a liquid crystal composition is added with a photopolymerizable compound.
- a liquid crystal composition is added with a photopolymerizable compound.
- An object of the present invention is to solve the problems of the prior art described above. Specifically, an object of the present invention is to provide a polymerizable compound having improved solubility in a liquid crystal aligning agent or liquid crystal.
- the present inventors have improved storage stability in varnish by using a novel polymerizable compound having a mother nucleus substituted with a halogen atom, and further liquid crystal It has been found that the solubility in is improved.
- the present invention is based on such knowledge and has the following gist.
- Ar is a divalent organic group containing an aromatic ring having at least one halogen substituent, and n1 and n2 are each independently an integer of 1 to 10. 3.
- Ar is a polymerizable compound having a structure represented by the following formulas [2] to [4].
- (X represents a halogen group, particularly preferably a fluorine group.
- M 1 to m 6 are each independently an integer of 0 to 4
- m 7 and m 8 are each independently an integer of 0 to 3
- m 1 + M 2 is 1 or more and 8 or less
- m 3 + m 4 + m 5 is 1 or more and 12 or less
- m 6 + m 7 + m 8 is 1 or more and 10 or less
- a liquid crystal aligning agent comprising the polymerizable compound according to any one of 1 to 7 above and at least one polymer selected from polyimide and a polyimide precursor.
- a polymerizable compound having a divalent organic group containing an aromatic ring having at least one halogen substituent and two ⁇ -methylene- ⁇ -butyrolactone groups is used as a component of the liquid crystal alignment film material.
- it has high alignment fixing ability, improves storage stability in varnish, and further improves solubility in liquid crystal.
- the polymerizable compound of the present invention is represented by the following formula [1].
- Ar is a divalent organic group containing an aromatic ring having at least one halogen substituent, and n 1 and n 2 are each independently an integer of 1 to 10. From the viewpoint of ease of synthesis, n1 and n2 are preferably the same. Ar is preferably represented by the following formulas [2] to [4].
- X represents a halogen group, and a fluorine group is particularly preferable.
- m 1 to m 6 are each independently an integer of 0 to 4
- m 7 and m 8 are each independently an integer of 0 to 3
- m 1 + m 2 is from 1 to 8
- m 3 + m 4 + M 5 is 1 or more and 12 or less
- m 6 + m 7 + m 8 is 1 or more and 10 or less.
- X represents a fluorine group
- m 1 + m 2 is 1 or more and 3 or less
- m 3 + m 4 + m 5 is 1 or more and 4 or less
- m 6 + m 7 + m 8 is It is preferably 1 or more and 3 or less from the viewpoint of easiness of synthesis and economic efficiency. In any case, it is particularly preferably 1 or more and 2 or less. From the viewpoint of solubility, the substitution position of X is preferably such that Ar is asymmetric.
- the polymerizable compound of the present invention represented by the formula [1] can be synthesized by combining techniques in organic synthetic chemistry, and the synthesis method is not particularly limited. For example, as shown in [Reaction Scheme 1] below, cross coupling using aryl halides [2-A] to [2-D], organometallic reagents [3-A] to [3-B], and a transition metal catalyst The corresponding mother nucleus [4-A] to [4-C] is synthesized by reacting, and then reacted with the corresponding halide [8] in the presence of a base to synthesize an ether compound [9], and a metal reagent Can be made to react with an acrylic acid derivative [10].
- [Reaction Scheme 1] cross coupling using aryl halides [2-A] to [2-D], organometallic reagents [3-A] to [3-B], and a transition metal catalyst
- the corresponding mother nucleus [4-A] to [4-C] is synthe
- Ar 1, Ar 2 , and Ar 3 are each independently a divalent organic group having an aromatic ring, and at least one of Ar 1 , Ar 2 , and Ar 3 has at least one halogen substituent.
- the halogen group is preferably an F atom.
- M is B (OH) 2 or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl.
- Hal is Cl or Br, I, OTf.
- PG is a dimethyl acetal group, a diethyl acetal group, a 1,3-dioxane group, or a 1,3-dioxolane group.
- n is an integer of 1 to 10.
- X 1 is Cl, Br or I.
- X 2 is Cl or Br.
- Tf represents a triflate group, that is, a trifluoromersulfonyl group.
- F-containing biaryl compound [4-A] examples include the following biphenyl compounds [4-1] to [4-42] and phenylnaphthyl compounds [4-43] to [4-58].
- the F group-containing biphenyl compound [4-A] such as the above [4-1] to [4-41] includes an aryl halide [2-A] and an organometallic reagent [3-A] as shown below. It can be obtained by a cross-coupling reaction using a metal catalyst.
- X represents F
- Hal represents Br
- I or OTf
- M represents B (OH) 2 or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl.
- the amount of the aryl halide [2-A] and boronic acid derivative [3-A] represented by the above cross-coupling reaction is not particularly limited, but the aryl halide [2-A] 1
- the boronic acid derivative [3-A] is preferably used in an amount of 1.0 to 1.5 equivalents based on equivalents. Further, 1.0 to 1.5 equivalents of aryl halide [2-A] may be used per 1 equivalent of boronic acid derivative [3-A].
- the above coupling reaction uses an appropriate metal complex and a ligand as a catalyst. In some cases, the reaction proceeds without a ligand. Usually, a palladium complex or a nickel complex is used. As the catalyst, those having various structures can be used, but it is preferable to use a so-called low-valent palladium complex or nickel complex, particularly a zero-valent complex having a tertiary phosphine or tertiary phosphite as a ligand. Is preferred. In addition, an appropriate precursor that can be easily converted into a zero-valent complex in the reaction system can also be used.
- a complex containing no tertiary phosphine or tertiary phosphite as a ligand is mixed with a tertiary phosphine or tertiary phosphite, and the tertiary phosphine or tertiary phosphite is converted into a ligand. It is also possible to generate a low valence complex.
- tertiary phosphine or tertiary phosphite as a ligand examples include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenylphosphino) ethane, 1 , 3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphino) ferrocene, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, etc.
- Complexes containing a mixture of two or more of these ligands are also preferably used. It is also preferable to use a combination of a palladium complex not containing tertiary phosphine or tertiary phosphite, a complex containing tertiary phosphine or tertiary phosphite, and the above-mentioned ligand as a catalyst.
- Complexes containing no tertiary phosphine or tertiary phosphite used in combination with the above ligands include bis (benzylideneacetone) palladium, tris (benzylideneacetone) dipalladium, bis (acetonitrile) dichloropalladium, bis (benzo Nitrile) dichloropalladium, palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated carbon, nickel chloride, nickel iodide and the like, and as a complex already containing tertiary phosphine or tertiary phosphite as a ligand Are dimethylbis (triphenylphosphine) palladium, dimethylbis (diphenylmethylphosphine) palladium, (ethylene) bis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) pal
- Bases include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, methylamine, dimethyl Amine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, collidine, etc.
- sodium acetate, potassium acetate, lithium acetate and the like can also be used.
- the solvent is stable under the reaction conditions and is inert and does not interfere with the reaction.
- the reaction temperature is not particularly limited, but is usually ⁇ 90 to 200 ° C., preferably ⁇ 50 to 150 ° C., more preferably 40 to 120 ° C.
- the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 40 hours, more preferably 0.5 to 24 hours.
- the F-containing biphenyl compound [4-A] obtained as described above can be highly purified by purifying by slurry washing, recrystallization, silica gel column chromatography and the like after the reaction.
- the solvent used for washing is not particularly limited.
- hydrocarbons such as hexane, heptane or toluene, halogenated hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene, diethyl ether, tetrahydrofuran or 1,4 -Ethers such as dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, alcohols such as methanol or ethanol, 2-propanol, and mixtures thereof.
- hydrocarbons such as hexane, heptane or toluene
- halogenated hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene
- diethyl ether diethyl ether
- tetrahydrofuran or 1,4 -Ethers
- the solvent used for recrystallization is not particularly limited as long as the F-containing biphenyl compound [4-A] dissolves upon heating and precipitates upon cooling.
- hydrocarbons such as hexane, heptane or toluene, chloroform, 1, 2 -Halogen hydrocarbons such as dichloroethane or chlorobenzene, ethers such as diethyl ether, tetrahydrofuran or 1,4-dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile Alcohols such as methanol or ethanol, 2-propanol, and mixtures thereof, preferably ethyl acetate, tetrahydrofuran, toluene and hexane.
- Compound [4-42] is commercially available.
- the F-containing phenylnaphthyl compound [4-A] such as [4-43] to [4-50] includes an aryl halide [2-A] and an organometallic reagent [3-A]. Can be obtained by a cross-coupling reaction using a metal catalyst such as Pd.
- X represents F.
- M represents B (OH) 2 or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl.
- the amount of the aryl halide [2-A] and the boronic acid derivative [3-A] used in the cross-coupling reaction is not particularly limited, but boron is equivalent to 1 equivalent of the aryl halide [2-A]. It is preferable to use 1.0 to 1.5 equivalents of the acid derivative [3-A]. Further, 1.0 to 1.5 equivalents of aryl halide [2-A] may be used per 1 equivalent of boronic acid derivative [3-A].
- the above coupling reaction uses an appropriate metal complex and a ligand as a catalyst.
- the kind of the catalyst and the ligand is the same as the F-containing biphenyl compound synthesis method.
- the base is the same as the method for synthesizing F-containing biphenyl compounds.
- the solvent is the same as in the F-containing biphenyl compound synthesis method.
- the reaction temperature is not particularly limited, but is usually ⁇ 90 to 200 ° C., preferably ⁇ 50 to 150 ° C., more preferably 40 to 120 ° C.
- the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 40 hours, more preferably 0.5 to 24 hours.
- the F-containing phenylnaphthyl compound [4-A] obtained as described above can be highly purified by purifying by slurry washing, recrystallization, silica gel column chromatography and the like after the reaction.
- the method is the same as the F-containing biphenyl compound synthesis method.
- the F-containing phenyl-naphthyl compound [4-A] such as the above [4-51] to [4-58] includes an aryl halide [2-A] and an organometallic reagent [3-A] as shown below. ] Can be obtained by a cross-coupling reaction using a metal catalyst such as Pd.
- X represents F.
- M represents B (OH) 2 or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl.
- the amount of the aryl halide [2-A] and the boronic acid derivative [3-A] used in the cross-coupling reaction is not particularly limited, but boron is equivalent to 1 equivalent of the aryl halide [2-A]. It is preferable to use 1.0 to 1.5 equivalents of an acid derivative. Further, 1.0 to 1.5 equivalents of aryl halide may be used per 1 equivalent of boronic acid derivative [3-A].
- the above coupling reaction uses an appropriate metal complex and a ligand as a catalyst.
- the kind of the catalyst and the ligand is the same as the F-containing biphenyl compound synthesis method.
- the base is the same as the method for synthesizing F-containing biphenyl compounds.
- the solvent is the same as in the F-containing biphenyl compound synthesis method.
- the reaction temperature is not particularly limited, but is usually ⁇ 90 to 200 ° C., preferably ⁇ 50 to 150 ° C., more preferably 40 to 120 ° C.
- the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 40 hours, more preferably 0.5 to 24 hours.
- the F-containing phenylnaphthyl compound [4-A] obtained as described above can be highly purified by purifying by slurry washing, recrystallization, silica gel column chromatography and the like after the reaction.
- the method is the same as the F-containing biphenyl compound synthesis method.
- examples of the F-containing terphenyl compound [4-B] obtained by the coupling reaction of [Reaction Formula 1] include the following compounds.
- the F-containing terphenyl compound [4-B] has a structure in which the left and right benzene rings (A) are the same as the middle benzene ring (B) in the tricyclic structure.
- the F group-containing terphenyl compound [4-B] such as [4-59] to [4-99] includes an aryl halide [2-B] and an organometallic reagent [3-A]. ], By carrying out a cross-coupling reaction using a metal catalyst.
- X represents F
- Hal represents Br
- I or OTf
- M represents B (OH) 2 or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl.
- the amount of the aryl halide [2-B] and the boronic acid derivative [3-A] represented by the above cross-coupling reaction is not particularly limited, but boron is equivalent to 1 equivalent of the aryl halide [2-B]. It is preferable to use 2.0 to 2.5 equivalents of the acid derivative [3-A].
- the above coupling reaction uses an appropriate metal complex and a ligand as a catalyst.
- the kind of the catalyst and the ligand is the same as the F-containing biphenyl compound synthesis method.
- the base is the same as the method for synthesizing F-containing biphenyl compounds.
- the solvent is the same as in the F-containing biphenyl compound synthesis method.
- the reaction temperature is not particularly limited, but is usually ⁇ 90 to 200 ° C., preferably ⁇ 50 to 150 ° C., more preferably 40 to 120 ° C.
- the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 40 hours, more preferably 0.5 to 24 hours.
- the F-containing terphenyl compound [4-B] obtained as described above can be highly purified by purifying by slurry washing, recrystallization, silica gel column chromatography and the like after the reaction.
- the method is the same as the F-containing biphenyl compound synthesis method.
- the F group-containing terphenyl compound [4-C] such as the above [4-100] to [4-246] includes an aryl halide [2-C] and an organometallic reagent [3-A] as shown below. And a cross-coupling reaction using a metal catalyst, and a cross-coupling reaction is performed again with the obtained aryl halide [2-D] and organometallic reagent [3-B].
- the organometallic reagent [3-A] and the organometallic reagent [3-B] are organometallic reagents having different structures.
- X represents F.
- M represents B (OH) 2 or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl.
- [3-A] and [3-B] are different boronic acid derivatives.
- aryl halide [2-C] and boronic acid derivative [3-A] represented by the above cross-coupling reaction is not particularly limited, but boron is equivalent to 1 equivalent of aryl halide [2-C]. It is preferable to use 1.0 to 1.2 equivalents of the acid derivative [3-A]. Further, the same usage amount is preferable for the subsequent Suzuki-Miyaura reaction.
- the above coupling reaction uses an appropriate metal complex and a ligand as a catalyst.
- the kind of the catalyst and the ligand is the same as the F-containing biphenyl compound synthesis method.
- the base is the same as the method for synthesizing F-containing biphenyl compounds.
- the solvent is the same as in the F-containing biphenyl compound synthesis method.
- the reaction temperature is not particularly limited, but is usually ⁇ 90 to 200 ° C., preferably ⁇ 50 to 150 ° C., more preferably 40 to 120 ° C.
- the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 40 hours, more preferably 0.5 to 24 hours.
- the F-containing terphenyl compound [4-C] obtained as described above can be highly purified by purifying by slurry washing, recrystallization, silica gel column chromatography and the like after the reaction.
- the method is the same as the F-containing biphenyl compound synthesis method.
- the F-containing ether compound [9] comprises an aromatic compound [4-A] to [4-C] containing a phenolic hydroxyl group and an alkyl halide [8] in the presence of a base as necessary. It can be obtained by reacting in the presence of an additive.
- Ar 1, Ar 2 , and Ar 3 are each independently a divalent organic group having an aromatic ring, and at least one of Ar 1 , Ar 2 , and Ar 3 has at least one halogen substituent.
- the halogen group is preferably an F atom.
- n1 is an integer of 1 to 10.
- X 1 is Cl, Br or I
- PG is a dimethyl acetal group, a diethyl acetal group, a 1,3-dioxane group or a 1,3-dioxolane group.
- inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate and the like can be used.
- Sodium carbonate and potassium carbonate are preferable.
- Additives can be used for the purpose of accelerating the reaction rate.
- potassium iodide, sodium iodide, quaternary ammonium salt, crown ether and the like can be used as the additive.
- the solvent is stable under the reaction conditions and is inert and does not interfere with the reaction.
- solvents can be appropriately selected in consideration of the ease of reaction and the like.
- the above solvents can be used alone or in combination of two or more.
- Acetone and an aprotic polar organic solvent are preferable.
- the reaction temperature is not particularly limited, but is usually ⁇ 90 to 200 ° C., preferably 40 to 150 ° C.
- the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 60 hours.
- the F-containing ether compound [9] obtained as described above can be highly purified by purifying by slurry washing, recrystallization, silica gel column chromatography and the like after the reaction.
- the solvent used for washing is not particularly limited.
- hydrocarbons such as hexane, heptane or toluene, halogenated hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene, diethyl ether, tetrahydrofuran or 1,4 -Ethers such as dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, alcohols such as methanol or ethanol, 2-propanol, and mixtures thereof.
- alcohols such as methanol or ethanol and 2-propanol are used.
- the solvent used for recrystallization is not particularly limited as long as the F-containing ether compound [9] dissolves upon heating and precipitates upon cooling.
- hydrocarbons such as hexane, heptane or toluene, chloroform, 1,2-dichloroethane, etc.
- halogen-based hydrocarbons such as chlorobenzene, ethers such as diethyl ether, tetrahydrofuran or 1,4-dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, Examples thereof include alcohols such as methanol or ethanol and 2-propanol, and mixtures thereof, preferably alcohols such as ethyl acetate, tetrahydrofuran, toluene, methanol or ethanol and 2-propanol, hexane or the like. Mixtures thereof.
- the ⁇ -methylene- ⁇ -butyrolactone compound [1] can be synthesized by combining methods in organic synthetic chemistry, and the synthesis method is not particularly limited. As shown below, it can be synthesized by reacting an aldehyde or ketone, acetal, ketal with a metal reagent and an acrylic acid derivative under acidic conditions (reference: for example, P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530 (1990)).
- Ar 1, Ar 2 , and Ar 3 are each independently a divalent organic group having an aromatic ring, and at least one of Ar 1 , Ar 2 , and Ar 3 has at least one halogen substituent.
- the halogen group is preferably an F atom.
- n1 is an integer of 1 to 10.
- R includes a hydrogen atom or a C1-4 alkyl group.
- PG is a dimethyl acetal group, a diethyl acetal group, a 1,3-dioxane group or a 1,3-dioxolane group.
- X 2 is Cl or Br.
- acrylic acid derivative [10] represented by the lactone ring synthesis 2- (chloromethyl) acrylic acid, 2- (chloromethyl) methyl acrylate, 2- (chloromethyl) ethyl acrylate, 2- (bromomethyl) Acrylic acid, methyl 2- (bromomethyl) acrylate, ethyl 2- (bromomethyl) acrylate, and the like can be used.
- the amount of acrylic acid derivative [10] used is not particularly limited, but it is preferable to use 2.0 to 2.5 equivalents of acrylic acid derivative per 1 equivalent of ether compound [9].
- tin compounds such as tin powder, anhydrous tin chloride, tin chloride dihydrate, tin chloride pentahydrate, indium powder, zinc powder and the like can be used.
- an inorganic acid aqueous solution such as hydrochloric acid, sulfuric acid, phosphoric acid and ammonium chloride, an acidic resin such as Amberlyst® 15, and an organic acid such as p-toluenesulfonic acid, acetic acid and formic acid can be used.
- the solvent is stable under the reaction conditions and is inert and does not interfere with the reaction.
- the reaction temperature is not particularly limited, but is usually ⁇ 90 to 200 ° C., preferably 20 to 100 ° C.
- the reaction time is usually 0.05 to 200 hours, preferably 0.5 to 60 hours.
- the ⁇ -methylene- ⁇ -butyrolactone compound [1] obtained as described above can be highly purified by purifying by slurry washing, recrystallization, silica gel column chromatography and the like after the reaction.
- the solvent used for washing is not particularly limited.
- hydrocarbons such as hexane, heptane or toluene, halogenated hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene, diethyl ether, tetrahydrofuran or 1,4 -Ethers such as dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, alcohols such as methanol or ethanol, 2-propanol, and mixtures thereof.
- alcohols such as methanol or ethanol and 2-propanol are used.
- the solvent used for recrystallization is not particularly limited as long as the ⁇ -methylene- ⁇ -butyrolactone compound [1] dissolves upon heating and precipitates upon cooling.
- hydrocarbons such as hexane, heptane or toluene, chloroform, 1 Halogen hydrocarbons such as 1,2-dichloroethane or chlorobenzene, ethers such as diethyl ether, tetrahydrofuran or 1,4-dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, acetonitrile or propionitrile, etc.
- Nitriles such as methanol or ethanol, 2-propanol, and mixtures thereof, and preferably alcohols such as ethyl acetate, tetrahydrofuran, toluene, methanol or ethanol, 2-propanol, etc. Hexane or a mixture thereof.
- the present application also provides a liquid crystal aligning agent containing a polymerizable compound having improved solubility in a liquid crystal aligning agent or liquid crystal.
- the liquid crystal aligning agent of the present application is [I] at least one polymerizable compound selected from the group consisting of compounds represented by the formula [1], and [II] at least one polymer selected from polyimide and a polyimide precursor. Containing.
- At least one polymer selected from polyimide and polyimide precursor > [II]
- a polyimide or a polyimide precursor that can be conventionally known or used in the future for a liquid crystal aligning agent can be used.
- At least one polymer selected from polyimides and polyimide precursors may have (I) a side chain for vertically aligning liquid crystals for PSA type liquid crystal displays. ⁇ (I) Side chain for vertically aligning liquid crystal >> (I) A side chain that aligns liquid crystal vertically (hereinafter also referred to as side chain A) is a side chain that has the ability to align liquid crystal molecules vertically with respect to the substrate. Its structure is not limited.
- a side chain for example, a long-chain alkyl group or a fluoroalkyl group, a cyclic group having an alkyl group or a fluoroalkyl group at the terminal, a steroid group, or the like is known, and is preferably used in the present invention.
- These groups may be directly bonded to the main chain of the polyimide or polyimide precursor as long as they have the above-mentioned ability, or may be bonded via an appropriate bonding group.
- Examples of the side chain A include those represented by the following formula (a).
- l, m and n each independently represents an integer of 0 or 1
- R 1 represents an alkylene group having 2 to 6 carbon atoms, —O—, —COO—, —OCO—, —NHCO—, —CONH—, or an alkylene-ether group having 1 to 3 carbon atoms
- R 2 , R 3 and R 4 each independently represents a phenylene group or a cycloalkylene group
- R 5 represents a hydrogen atom
- It represents an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a macrocyclic substituent composed thereof.
- R 1 in the formula (a) is an alkylene group having 2 to 6 carbon atoms, —O—, —COO—, —OCO—, —NHCO—, —CONH—, or an alkylene ether having 1 to 3 carbon atoms. Represents a group. Among these, from the viewpoint of ease of synthesis, —O—, —COO—, —CONH—, and an alkylene-ether group having 1 to 3 carbon atoms are preferable.
- R 2 , R 3 and R 4 in the formula (a) each independently represent a phenylene group or a cycloalkylene group. From the viewpoint of ease of synthesis and ability to align liquid crystals vertically, combinations of l, m, n, R 2 , R 3 and R 4 shown in the following table are preferred.
- R 5 in the formula (a) represents a hydrogen atom, an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a macrocyclic substituent composed thereof.
- the structure of R 5 is preferably a hydrogen atom, an alkyl group having 2 to 14 carbon atoms or a fluorine-containing alkyl group, more preferably a hydrogen atom or carbon atom number. 2 to 12 alkyl groups or fluorine-containing alkyl groups.
- R 5 is preferably an alkyl group having 12 to 22 carbon atoms, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or the like.
- a macrocyclic substituent more preferably an alkyl group having 12 to 20 carbon atoms or a fluorine-containing alkyl group.
- the ability to align the liquid crystal vertically depends on the structure of the side chain A described above, but generally, as the amount of the side chain A contained in the polymer increases, the ability to align the liquid crystal vertically increases and decreases. Go down. Further, the side chain A containing a cyclic structure tends to align the liquid crystal vertically even with a small content as compared with the side chain A of the long-chain alkyl group.
- the amount of the side chain A in the polyimide or polyimide precursor used in the present invention is not particularly limited as long as the liquid crystal alignment film can vertically align the liquid crystal.
- the amount of the side chain A is preferably as small as possible within the range in which the vertical alignment can be maintained. .
- the polyimide or polyimide precursor has (II) a photoreactive side chain in addition to the above-mentioned (I) side chain for vertically aligning liquid crystal for SC-PVA type liquid crystal display. Is good.
- a photoreactive side chain (hereinafter also referred to as side chain B) is a crosslinkable side chain having a functional group (hereinafter also referred to as photocrosslinking group) that can react by irradiation with ultraviolet rays to form a covalent bond, or A photoradical generating side chain having a functional group capable of generating radicals upon irradiation with ultraviolet rays, and its structure is not limited as long as it has this ability.
- a side chain containing a vinyl group, an acrylic group, a methacryl group, an anthracenyl group, a cinnamoyl group, a chalcone group, a coumarin group, a maleimide group, a stilbene group or the like as a photocrosslinking group is known. And is also preferably used in the present invention.
- a specific structure that generates radicals by ultraviolet irradiation is also preferably used.
- These groups may be directly bonded to the main chain of the polyimide or polyimide precursor as long as they have the above-mentioned ability, or may be bonded via an appropriate bonding group.
- Examples of the side chain B include those represented by the following formulas (b-1) to (b-3).
- R 6 represents —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ) —, —CON (CH 3 ) —, —N (CH 3 ) CO—, wherein R 7 is cyclic, unsubstituted or substituted with a fluorine atom having 1 to 20 carbon atoms
- R 8 represents —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —NH—, —N (CH 3 ) —, —CON (CH 3 ) —, —N (CH 3 ).
- R 9 is a styryl group, —CR 10 ⁇ CH 2 group, a carbocycle, a heterocycle, or a structure represented by the following formulas R9-1 to R9-31
- R 10 represents a hydrogen atom or a methyl group which may be substituted with a fluorine atom.
- the above linking group represented by R 6 in the formula (b-1) can be formed by a general organic synthetic method, but from the viewpoint of ease of synthesis, —CH 2 —, —O—, —COO—, —NHCO—, —NH—, and —CH 2 O— are preferred.
- carbocycle and heterocycle in the definition of R 7 in formula (b-1) include the following structures, but are not limited thereto.
- linking groups represented by R 8 in the formula (b-1) from the viewpoint of ease of synthesis, —CH 2 —, —O—, —COO—, —OCO—, NHCO—, — NH-, carbocycle or heterocycle is preferred.
- Specific examples of the carbocycle and heterocycle are the same as the carbocycle and heterocycle in the definition of R 7 .
- R 9 in formula (b-1) represents a styryl group, —CR 10 ⁇ CH 2 , a carbocycle, a heterocyclic ring, or a structure represented by the above formulas R9-1 to R9-31, and R 10 represents a hydrogen atom or It represents a methyl group which may be substituted with a fluorine atom.
- R 9 is more preferably a styryl group, —CH ⁇ CH 2 , —C (CH 3 ) ⁇ CH 2, or the above formulas R9-2, R9-12, or R9-15.
- R 9 is —CH ⁇ CH 2 or —C (CH 3 ) ⁇ CH 2 and R 8 is —OCO—, an acryl group or a methacryl group is formed, but such a case is also preferable.
- the side chain represented by the formula (b-2) is a side chain having a cinnamoyl structure and a methacrylic structure at the same time.
- R 10 represents a group selected from —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, and —CO—.
- R 11 is an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are , May be replaced by a fluorine atom or an organic group.
- R 11 may be substituted with —CH 2 — when any of the following groups are not adjacent to each other; —O—, —NHCO—, —CONH—, — COO—, —OCO—, —NH—, —NHCONH—, —CO—.
- R 12 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—, or a single bond.
- R 13 represents a photocrosslinkable group such as a cinnamoyl group, a chalcone group, or a coumarin group.
- R 14 is a single bond, or an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more of the alkylene group, divalent carbocycle or heterocycle
- the hydrogen atom may be replaced with a fluorine atom or an organic group.
- R 14 may be substituted with —CH 2 — when any of the following groups are not adjacent to each other: —O—, —NHCO—, —CONH—, — COO—, —OCO—, —NH—, —NHCONH—, —CO—.
- R 15 represents a photopolymerizable group selected from either an acryl group or a methacryl group.
- Specific examples of the side chain represented by the formula (b-2) include the following structures (in the formula, R represents a hydrogen atom or a methyl group which may be substituted with fluorine). ).
- Formula (b-3) is a side chain that generates radicals by ultraviolet irradiation.
- Ar 4 represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, which may be substituted with an organic group, and a hydrogen atom may be replaced with a halogen atom.
- R 16 and R 17 are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group or a phenethyl group. In the case of an alkyl group or an alkoxy group, R 16 and R 17 form a ring. May be.
- T 1 and T 2 are each independently a single bond or —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ).
- S is an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted by a fluorine atom (provided that the alkylene group is —CH 2 — or —CF 2 — may be optionally replaced by —CH ⁇ CH—, and may be replaced by any of these groups when any of the following groups is not adjacent to each other: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring, a divalent heterocyclic ring, and n2 is 0 or 1; Represents a structure selected from
- R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 3 represents —CH 2 —, —NR—, —O—, —S—.
- Specific examples of the side chain represented by the formula (b-3) include the following structures.
- the amount of the side chain B is not particularly limited as long as the response speed of the liquid crystal in the liquid crystal display element can be increased.
- a polyamic acid which is a kind of polyimide precursor having a side chain A is either a side chain A or a side chain A among diamine and tetracarboxylic anhydride as raw materials, It can be obtained by reacting raw materials.
- the method using a diamine compound having a side chain A is preferable from the viewpoint of ease of raw material synthesis.
- the polyamic acid having a side chain A and a side chain B is either a side chain A or a side chain B, or only one side chain A is a raw material of diamine and tetracarboxylic anhydride.
- the other has only the side chain B, either one has the side chain A and the side chain B and the other has the side chain A, either one has the side chain A and the side chain B And the other has side chain B, or both have side chain A and side chain B, and can be obtained by reacting the raw materials.
- the method using a diamine compound having a side chain A, a diamine compound having a side chain B, and a tetracarboxylic acid having no side chain A or side chain B is preferable from the viewpoint of ease of raw material synthesis.
- the diamine compound having the side chain A will be described, and then the diamine compound having the side chain B will be described.
- ⁇ Diamine compound having side chain A> As a diamine compound having a side chain A (hereinafter also referred to as diamine A), the diamine side chain has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a macrocyclic substituent composed thereof.
- a diamine can be mentioned as an example. Specific examples include diamines having a side chain represented by the formula (a). More specifically, examples include diamines represented by the following formulas (1), (3), (4), and (5), but are not limited thereto.
- the definitions of l, m, n and R 1 to R 5 in the formula (1) are the same as those in the formula (a).
- each of A 10 independently represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH.
- - represents, a 11 represents a single bond or a phenylene radical, a represents the side chain a, a 'is an alkyl group, a fluorine-containing alkyl group, aromatic ring, aliphatic ring, any structure selected from heterocycle It represents a macrocyclic substituent composed of a combination.
- a 14 is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom
- a 15 is a 1,4-cyclohexylene group or 1,4-phenylene
- a 16 is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A 3 )
- a 17 is an oxygen atom or —COO— * (wherein , “*” Is a bond with (CH 2 ) a 2 ).
- a 1 is an integer of 0 or 1
- a 2 is an integer of 2 to 10
- a 3 is an integer of 0 or 1.
- the bonding position of the two amino groups (—NH 2 ) in the formula (1) is not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine compound, the positions 2, 4 or 3, 5 are more preferable.
- a 1 each independently represents an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group.
- a 2 each independently represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—.
- a 3 are each independently an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.
- a 4 each independently represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, — CH 2 O -, - OCH 2 -, or -CH 2 - indicates, a 5 are each independently 1 to 22 alkyl group carbon atoms, an alkoxy group, a fluorine-containing alkyl group or fluorine-containing alkoxy group.
- a 6 each independently represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, — CH 2 O—, —OCH 2 —, —CH 2 —, —O—, or —NH—
- a 7 represents a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group , An acetoxy group, or a hydroxyl group.
- a 8 each independently represents an alkyl group having 3 to 12 carbon atoms, and cis-trans isomerism of 1,4-cyclohexylene is trans isomerism, respectively. Is the body.
- a 9 is each independently an alkyl group having 3 to 12 carbon atoms, and cis-trans isomerism of 1,4-cyclohexylene is trans isomerism, respectively. Is the body.
- diamines represented by the formula (3) the following formula [A-25] ⁇ formula [A-30]
- a 12 are, -COO -, - OCO -, - CONH -, - NHCO- , —CH 2 —, —O—, —CO—, or —NH—
- a 13 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group. Yes, but not limited to this.
- diamine represented by the formula (4) examples include diamines represented by the following formulas [A-31] to [A-32], but are not limited thereto.
- the diamines of A-16], [A-21] and [A-22] are preferred.
- the diamine compounds can be used alone or in combination of two or more depending on the liquid crystal alignment properties, pretilt angle, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.
- the diamine A should be 5-70 mol%, preferably 10-50 mol%, more preferably 20-50 mol%. .
- diamine compounds having side chain B examples include vinyl group, acrylic group, methacryl group, anthracenyl group, cinnamoyl group, chalconyl group, coumarin group, maleimide group, stilbene group, etc.
- a diamine having a specific structure capable of generating radicals upon irradiation with ultraviolet rays Specific examples include diamines having side chains represented by the formulas (b-1) to (b-3). As a specific example, it is represented by the following general formula (2) (the definitions of R 6 , R 7 , R 8 , R 9 and R 10 in formula (2) are the same as those in formula (b-1)).
- a diamine can be mentioned, it is not limited to this.
- the bonding position of the two amino groups (—NH 2 ) in the formula (2) is not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine compound, the positions 2, 4 or 3, 5 are more preferable. Specific examples include the following compounds, but are not limited thereto.
- X independently represents a linking group selected from —C—, —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, and l, m, n, Each independently represents an integer of 0 to 20, k represents an integer of 1 to 20, and R represents a hydrogen atom or a methyl group.
- the diamine compound may be one kind or two depending on the liquid crystal orientation, the pretilt angle, the voltage holding characteristics, the accumulated charge characteristics, and the liquid crystal response speed when the liquid crystal display element is used. A mixture of more than one can also be used.
- the diamine B is greater than 0% and not more than 95 mol%, preferably 20-80 mol%, more preferably 40-70 mol%. Good.
- the polyamic acid used in the present invention can be used in combination with other diamine compounds other than diamine A and diamine B as the diamine component as long as the effects of the present invention are not impaired. Specific examples are given below.
- the above-mentioned other diamine compounds may be used alone or in combination of two or more depending on the properties such as the liquid crystal orientation, the pretilt angle, the voltage holding property, and the accumulated charge when the liquid crystal alignment film is used.
- tetracarboxylic dianhydride In the synthesis of the polyamic acid used in the present invention, the tetracarboxylic dianhydride to be reacted with the diamine component is not particularly limited. Specific examples are given below.
- the tetracarboxylic dianhydride can be used singly or in combination of two or more according to properties such as liquid crystal alignment properties, voltage holding properties, and accumulated charges when formed into a liquid crystal alignment film.
- ⁇ Synthesis of polyamic acid> In obtaining a polyamic acid by a reaction between a diamine component and tetracarboxylic dianhydride, a known synthesis method can be used. In general, the diamine component and tetracarboxylic dianhydride are reacted in an organic solvent. The reaction between the diamine component and tetracarboxylic dianhydride is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.
- the organic solvent used in the above reaction is not particularly limited as long as the produced polyamic acid dissolves. Furthermore, even if it is an organic solvent which does not dissolve a polyamic acid, it may be mixed with the said solvent and used as long as the produced polyamic acid does not precipitate. In addition, since the water
- the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is used as it is or in an organic solvent.
- a method of adding by dispersing or dissolving in a solvent a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine component.
- the method of adding alternately etc. is mentioned, You may use any of these methods.
- the diamine component or tetracarboxylic dianhydride component when they are composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually.
- the body may be mixed and reacted to form a high molecular weight body.
- the temperature at the time of reacting the diamine component and the tetracarboxylic dianhydride component can be selected arbitrarily, and is, for example, in the range of ⁇ 20 ° C. to 150 ° C., preferably ⁇ 5 ° C. to 100 ° C.
- the reaction can be carried out at any concentration, for example 1 to 50% by mass, preferably 5 to 30% by mass.
- the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component can be selected according to the molecular weight of the polyamic acid to be obtained. Similar to the normal polycondensation reaction, the molecular weight of the polyamic acid produced increases as the molar ratio approaches 1.0. If it shows a preferable range, it is 0.8 to 1.2.
- the method for synthesizing the polyamic acid used in the present invention is not limited to the above-described method, and, like the general polyamic acid synthesis method, instead of the tetracarboxylic dianhydride, a tetracarboxylic acid having a corresponding structure is used.
- the corresponding polyamic acid can also be obtained by reacting by a known method using a tetracarboxylic acid derivative such as acid or tetracarboxylic acid dihalide.
- Examples of the method for imidizing the polyamic acid to form a polyimide include thermal imidization in which a polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.
- the imidization ratio from polyamic acid to polyimide is not necessarily 100%.
- the temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the outside of the system.
- the catalytic imidation of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a polyamic acid solution and stirring at -20 to 250 ° C., preferably 0 to 180 ° C.
- the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
- the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
- Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
- the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
- the reaction solution may be poured into a poor solvent and precipitated.
- the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water.
- the polymer precipitated in a poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating.
- the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced.
- the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
- the liquid crystal aligning agent of the present invention has the above [I] polymerizable compound; and the above [II] at least one polymer selected from polyimides and polyimide precursors, in addition to the [I] and [II] components.
- the resin component for forming a resin film may be included.
- the content of all the resin components is 1% by mass to 20% by mass, preferably 3% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass in 100% by mass of the liquid crystal aligning agent.
- all of the above resin components may be polyimide or polyimide precursor having side chain A, or polyimide or polyimide precursor having side chain A and side chain B.
- a mixture of these may be used, and other polymers may be further mixed.
- the content of the other polymer in the resin component is preferably 0.5% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass.
- examples of such other polymers include polyimide or polyimide precursor having no side chain B, polyimide or polyimide precursor not having side chain A and side chain B at the same time. It is not limited.
- the molecular weight of the polymer of the above resin component is the weight measured by GPC (Gel Permeation Chromatography) method in consideration of the strength of the coating film obtained therefrom, workability at the time of coating film formation, and uniformity of the coating film
- the average molecular weight is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.
- the organic solvent used for the liquid crystal aligning agent of this invention will not be specifically limited if it is an organic solvent in which the resin component mentioned above is dissolved.
- This organic solvent may be one type of solvent or a mixed solvent of two or more types. If the specific example of an organic solvent is given dare, the organic solvent illustrated by the said polyamic acid synthesis can be mentioned.
- N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 3-methoxy-N, N-dimethylpropanamide dissolve resin components. From the viewpoint of sex.
- the solvent as shown below improves the uniformity and smoothness of the coating film, it is preferable to use the solvent by mixing it with a solvent having high solubility of the resin component.
- a solvent having high solubility of the resin component For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, Ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-buty
- the liquid crystal aligning agent may contain components other than those described above. Examples thereof include compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, and compounds that improve the adhesion between the liquid crystal aligning film and the substrate.
- Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.).
- the proportions used are preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part per 100 parts by mass of the resin component contained in the liquid crystal aligning agent. Part by mass.
- the compound that improves the adhesion between the liquid crystal alignment film and the substrate include a functional silane-containing compound and an epoxy group-containing compound.
- a functional silane-containing compound and an epoxy group-containing compound For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N
- a phenol compound such as 2,2′-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane or tetra (methoxymethyl) bisphenol is added. Also good.
- the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.
- the liquid crystal aligning agent used in the present invention is a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired. Substances may be added.
- ⁇ Liquid crystal alignment film> For example, after apply
- the substrate to be used is not particularly limited as long as it is a highly transparent substrate, glass plate, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, Trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose, acetate butyrate cellulose, and the like can be used.
- a substrate on which an ITO (Indium Tin Oxide) electrode or the like for driving a liquid crystal is formed from the viewpoint of simplifying the process.
- an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
- the method for applying the liquid crystal aligning agent is not particularly limited, and examples thereof include screen printing, offset printing, flexographic printing, and other printing methods, ink jet methods, spray methods, roll coating methods, dip, roll coaters, slit coaters, and spinners. From the standpoint of productivity, the transfer printing method is widely used industrially, and is preferably used in the present invention.
- the coating film formed by applying the liquid crystal aligning agent by the above method can be baked to obtain a cured film.
- the drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, the drying process is performed. It is preferable.
- the drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like. For example, a method of drying on a hot plate at a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C., for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes.
- the firing temperature of the coating film formed by applying the liquid crystal aligning agent is not limited, and can be performed at any temperature of, for example, 100 to 350 ° C., preferably 120 ° C. to 300 ° C., more preferably 150 to 250 ° C. Firing can be performed at an arbitrary time of 5 minutes to 240 minutes. The time is preferably 10 minutes to 90 minutes, more preferably 20 minutes to 90 minutes. Heating can be performed by a generally known method such as a hot plate, a hot air circulating furnace, an infrared furnace, or the like.
- the thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 to 300 nm, more preferably 10 to 120 nm.
- the liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method and then preparing a liquid crystal cell by a known method.
- the liquid crystal display element include two substrates disposed so as to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal aligning agent provided between the substrate and the liquid crystal layer.
- a vertical alignment type liquid crystal display device comprising a liquid crystal cell having the above-described liquid crystal alignment film.
- the liquid crystal aligning agent of the present invention is applied onto two substrates and baked to form a liquid crystal aligning film, and the two substrates are arranged so that the liquid crystal aligning films face each other.
- a liquid crystal layer composed of liquid crystal is sandwiched between two substrates, that is, a liquid crystal layer is provided in contact with the liquid crystal alignment film, and ultraviolet rays are applied while applying a voltage to the liquid crystal alignment film and the liquid crystal layer.
- This is a vertical alignment type liquid crystal display device including a liquid crystal cell to be manufactured.
- the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is used to irradiate ultraviolet rays while applying voltage to the liquid crystal alignment film and the liquid crystal layer to polymerize the polymerizable compound, and the light possessed by the polymer.
- a liquid crystal display device in which the alignment of the liquid crystal is more efficiently fixed and the response speed is remarkably improved by reacting the reactive side chains or the photoreactive side chain of the polymer with the polymerizable compound. It becomes.
- the substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed.
- a substrate on which a transparent electrode for driving liquid crystal As a specific example, the thing similar to the board
- a substrate provided with a conventional electrode pattern or protrusion pattern may be used, but in the liquid crystal display element of the present invention, the liquid crystal aligning agent of the present invention is used as the liquid crystal aligning agent for forming the liquid crystal aligning film. It is possible to operate even in a structure in which a line / slit electrode pattern of 1 to 10 ⁇ m, for example, is formed on one side substrate and a slit pattern or projection pattern is not formed on the opposite substrate. This process can be simplified and high transmittance can be obtained.
- a high-performance element such as a TFT type element
- an element in which an element such as a transistor is formed between an electrode for driving a liquid crystal and a substrate is used.
- a substrate In the case of a transmissive liquid crystal display element, it is common to use a substrate as described above. However, in a reflective liquid crystal display element, if only one substrate is used, an opaque substrate such as a silicon wafer may be used. Is possible. At that time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.
- the liquid crystal alignment film is formed by applying the liquid crystal aligning agent of the present invention on this substrate and baking it, and the details are as described above.
- the liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited, and a liquid crystal material used in a conventional vertical alignment method, for example, a negative type liquid crystal such as MLC-6608 or MLC-6609 manufactured by Merck Can be used.
- a known method can be exemplified. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one substrate so that the surface on which the liquid crystal alignment film is formed is on the inside. Then, the other substrate is bonded, and liquid crystal is injected under reduced pressure to seal.
- a liquid crystal cell can also be produced by a method in which the other substrate is bonded to the inside so as to be inside and sealed.
- the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
- the step of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer includes, for example, applying an electric field to the liquid crystal alignment film and the liquid crystal layer by applying a voltage between electrodes installed on the substrate. And applying ultraviolet rays while maintaining this electric field.
- the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p.
- the amount of ultraviolet irradiation is, for example, 1 to 60 J / cm 2 , preferably 40 J / cm 2 or less, and more preferably 20 J / cm 2 or less. It is preferable that the amount of ultraviolet irradiation be small because it is possible to suppress a decrease in reliability caused by the destruction of the liquid crystal and members constituting the liquid crystal display element, and the manufacturing efficiency is increased by reducing the ultraviolet irradiation time.
- the polymerizable compound when ultraviolet rays are applied while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, the polymerizable compound reacts to form a polymer, and the direction in which the liquid crystal molecules are tilted is memorized by this polymer.
- the response speed of the obtained liquid crystal display element can be increased.
- the photoreactive side chains of the polymer and the photoreactive side chains of the polymer react with the polymerizable compound.
- the response speed of the obtained liquid crystal display element can be increased.
- the liquid crystal aligning agent is not only useful as a liquid crystal aligning agent for producing a vertical alignment type liquid crystal display element such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display, but also by a rubbing process or a photo-alignment process. It can also be suitably used for applications of the liquid crystal alignment film to be produced.
- a vertically oriented diamine represented by the following formula DA-1 was synthesized by the method described in Japanese Patent No. 4085206.
- a vertically oriented diamine represented by the following formula DA-2 was synthesized by the method described in Japanese Patent No. 4466373.
- a vertically-aligned diamine represented by the following formula DA-3 was synthesized by the method described in Japanese Patent No. 5273035.
- the vertically oriented diamine represented by the following formula DA-4 was purchased from Tokyo Chemical Industry Co., Ltd.
- a vertically oriented diamine represented by the following formula DA-5 was synthesized by the method described in WO2009 / 093704.
- a photoreactive diamine represented by the following formula DA-6 was prepared as follows.
- the diamine represented by the following formula DA-7 was purchased from Wako Pure Chemical Industries.
- a radical-generating diamine represented by the following formula DA-8 was prepared as follows.
- the diamine represented by the following formula DA-9 was prepared by the method described later in “(Raw Material Synthesis Example 3) Synthesis of DA-9”.
- the molecular weight measurement conditions of polyimide are as follows. Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. Column: Column manufactured by Shodex (KD-803, KD-805), Column temperature: 50 ° C.
- GPC room temperature gel permeation chromatography
- N N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr ⁇ H 2 O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, Tetrahydrofuran (THF) at 10 ml / L), Flow rate: 1.0 ml / min, Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 9,000,150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight: about 12,000, 4) manufactured by Polymer Laboratory , 1,000, 1,000).
- the imidation ratio of polyimide was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard ⁇ 5 by Kusano Kagaku Co., Ltd.), add 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05% TMS mixture), and apply ultrasonic waves. To dissolve completely. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum.
- the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated
- x is the proton peak integrated value derived from the NH group of the amic acid
- y is the peak integrated value of the reference proton
- ⁇ is the proton of the NH group of the amic acid in the case of polyamic acid (imidation rate is 0%). This is the ratio of the number of reference protons to one.
- Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
- Step 1 Synthesis of 1- (4- (2,4-dinitrophenoxy) ethoxy) phenyl) -2-hydroxy-2-methylpropanone
- 2,4-dinitro 100.0 g of fluorobenzene [Mw: 186.10 g / mol], 0.538 mol
- 120.6 g of 2-hydroxy-4 ′-(2-hydroxyethoxy) -2-methylpropiophenone [Mw: 224.25 g / mol], 0.538 mol
- 81.7 g of triethylamine [Mw: 101.19 g / mol], 0.807 mol) and 1000 g of THF were added and refluxed for 24 hours.
- Step 2 Synthesis of 1- (4- (2,4-diaminophenoxy) ethoxy) phenyl) -2-hydroxy-2-methylpropanone (DA-8)
- DA-8 dinitrobenzene derivative obtained in Step 1 was added to a 1 L four-necked flask in 100.
- ethyl acetate was used to wash the flask and filtrate. Went. Subsequently, the aqueous phase is separated and the organic phase is recovered, and the recovered organic phase is washed with 350 g of pure water three times, dehydrated with magnesium sulfate, and then activated carbon (brand: special white birch dry product manufactured by Nippon Enviro Chemical) 2. 92 g was added and stirred at room temperature for about 30 minutes, followed by filtration and drying to obtain a crude product.
- activated carbon brand: special white birch dry product manufactured by Nippon Enviro Chemical
- the recovered organic phase was washed 3 times with 48.6 g of pure water, and the organic phase was dehydrated with magnesium sulfate and concentrated and dried. After drying, 12.1 mg of 2,6-di-tert-butyl-p-cresol is added to the recovered crude product, and 5.77 g of THF is added and heated at 45 ° C. to completely dissolve, 35.8 g of methanol. And was recrystallized at 5.0 ° C. However, since impurities were confirmed, 4.89 g of THF was added to the collected solid and completely dissolved by heating at 45 ° C., and 24.9 g of methanol was added and recrystallized at room temperature to obtain 6.37 g of RM2.
- reaction solution was diluted with 113 g of ethyl acetate, inorganic salts were removed by filtration, and the residue was washed with 70.5 g of ethyl acetate.
- inorganic salts were removed by filtration, and the residue was washed with 70.5 g of ethyl acetate.
- a small amount of white crystals was formed. Therefore, 70.5 g of ethyl acetate was added, and further washed with 141 g of pure water twice, and the organic phase was dehydrated with magnesium sulfate. , Filtered and dried.
- the reaction solution was added to 400 g of pure water to precipitate crystals, filtered, and the filtrate was slurry washed with 60.0 g of MeOH and filtered again to obtain a white solid.
- the obtained white solid was suspended in 500 g of THF, and 1.00 g of activated carbon (brand: special white rice dry product, Nippon Enviro Chemical) was added, stirred at 60 ° C. for 30 minutes, and then filtered while hot (45 ° C.).
- activated carbon brand: special white rice dry product, Nippon Enviro Chemical
- reaction solution was diluted with 50.0 g of ethyl acetate, the inorganic salt was filtered off, and the filtrate was diluted with 50.0 g of ethyl acetate, which was washed 3 times with 50.0 g of pure water at 50 ° C. . Thereafter, this organic phase was dehydrated with sodium sulfate, concentrated under reduced pressure to a total weight of 68.0 g, and the precipitated crystals were filtered. To the crude product, 5.0 g of THF and 20.0 g of MeOH were added and dissolved at 50 ° C., then cooled and stirred for a while.
- the reaction solution was concentrated under reduced pressure, 148 g of pure water was added, and the precipitated crystals were filtered and washed twice with 148 g of pure water.
- 118 g of THF and 118 g of MeOH were added to the crystals and dissolved at 50 ° C., then allowed to cool to room temperature and stirred for a while.
- the resulting crystals were filtered to obtain a crude product.
- 237 g of THF and 237 g of IPA were added to this crude product and dissolved at 60 ° C., and then cooled to room temperature and stirred for a while.
- NMP (44.0 g) was added to the obtained polyimide powder (A) -1 (6.0 g), and dissolved by stirring at 50 ° C. for 5 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D1 was obtained by stirring at room temperature for 5 hours.
- NMP (44.0 g) was added to the obtained polyimide powder (A) -2 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours.
- 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g), and BCS (30.0 g) were added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D2.
- NMP (44.0 g) was added to the obtained polyimide powder (A) -3 (6.0 g) and dissolved by stirring at 50 ° C. for 5 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D3 was obtained by stirring at room temperature for 5 hours.
- NMP (44.0 g) was added to the obtained polyimide powder (A) -4 (6.0 g) and dissolved by stirring at 50 ° C. for 5 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D4 was obtained by stirring at room temperature for 5 hours.
- NMP (44.0 g) was added to the obtained polyimide powder (A) -5 (6.0 g) and dissolved by stirring at 50 ° C. for 5 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D5 was obtained by stirring at room temperature for 5 hours.
- NMP (44.0 g) was added to the obtained polyimide powder (A) -6 (6.0 g), and dissolved by stirring at 50 ° C. for 5 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D6 was obtained by stirring at room temperature for 5 hours.
- NMP (44.0 g) was added to the obtained polyimide powder (A) -7 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D7 was obtained by stirring at room temperature for 5 hours.
- NMP (44.0 g) was added to the obtained polyimide powder (A) -8 (6.0 g), and dissolved by stirring at 50 ° C. for 5 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D8 was obtained by stirring at room temperature for 5 hours.
- NMP (44.0 g) was added to the obtained polyimide powder (A) -9 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D9 was obtained by stirring at room temperature for 5 hours.
- NMP (44.0 g) was added to the resulting polyimide powder (A) -10 (6.0 g), and dissolved by stirring at 50 ° C. for 5 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D11 was obtained by stirring at room temperature for 5 hours.
- NMP (44.0 g) was added to the obtained polyimide powder (A) -11 (6.0 g), and dissolved by stirring at 50 ° C. for 5 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D13 was obtained by stirring at room temperature for 5 hours.
- Example 1 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Synthesis Example 1 is added to 10.0 g of the liquid crystal aligning agent D1 obtained in Synthesis Example 13, and the mixture is stirred at room temperature for 3 hours. And dissolved to prepare liquid crystal aligning agent D15.
- the obtained liquid crystal aligning agent D15 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 2 liquid crystal aligning agent D16 was prepared by the method similar to Example 1 except the quantity of polymeric compound RM1 having been 0.09g (15 mass% with respect to solid content). When the obtained liquid crystal aligning agent D16 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 1 a liquid crystal aligning agent D17 was prepared in the same manner as in Example 1 except that the polymerizable compound RM2 obtained in Synthesis Example 2 was used instead of the polymerizable compound RM1.
- the obtained liquid crystal aligning agent D17 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 2 a liquid crystal aligning agent D18 was prepared in the same manner as in Example 2, except that the polymerizable compound RM2 obtained in Synthesis Example 2 was used instead of the polymerizable compound RM1.
- the obtained liquid crystal aligning agent D18 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 3 a liquid crystal aligning agent D19 was prepared in the same manner as in Example 1 except that the polymerizable compound RM3 obtained in Synthesis Example 3 was used instead of the polymerizable compound RM1.
- the obtained liquid crystal aligning agent D19 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 2 a liquid crystal aligning agent D20 was prepared in the same manner as in Example 2, except that the polymerizable compound RM3 obtained in Synthesis Example 3 was used instead of the polymerizable compound RM1.
- the obtained liquid crystal aligning agent D20 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 5 a liquid crystal aligning agent D21 was prepared in the same manner as in Example 1 except that the polymerizable compound RM4 obtained in Synthesis Example 4 was used instead of the polymerizable compound RM1.
- the obtained liquid crystal aligning agent D21 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 6 a liquid crystal aligning agent D22 was prepared in the same manner as in Example 2, except that the polymerizable compound RM4 obtained in Synthesis Example 4 was used instead of the polymerizable compound RM1.
- the obtained liquid crystal aligning agent D22 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 3 a liquid crystal aligning agent D23 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D2 obtained in Synthesis Example 14 was used instead of the liquid crystal aligning agent D1.
- the obtained liquid crystal aligning agent D23 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 4 In Example 1, a liquid crystal aligning agent D24 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D3 obtained in Synthesis Example 15 was used instead of the liquid crystal aligning agent D1. When the obtained liquid crystal aligning agent D24 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 5 a liquid crystal aligning agent D25 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D4 obtained in Synthesis Example 16 was used instead of the liquid crystal aligning agent D1.
- the obtained liquid crystal aligning agent D25 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 6 a liquid crystal aligning agent D26 was prepared in the same manner as in Example 2, except that the liquid crystal aligning agent D5 obtained in Synthesis Example 17 was used instead of the liquid crystal aligning agent D1.
- the obtained liquid crystal aligning agent D26 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 7 a liquid crystal aligning agent D27 was prepared in the same manner as in Example 2, except that the liquid crystal aligning agent D6 obtained in Synthesis Example 18 was used instead of the liquid crystal aligning agent D1.
- the obtained liquid crystal aligning agent D27 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 8 a liquid crystal aligning agent D28 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D7 obtained in Synthesis Example 19 was used instead of the liquid crystal aligning agent D1.
- the obtained liquid crystal aligning agent D28 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 9 a liquid crystal aligning agent D29 was prepared in the same manner as in Example 2, except that the liquid crystal aligning agent D10 obtained in Synthesis Example 22 was used instead of the liquid crystal aligning agent D1.
- the obtained liquid crystal aligning agent D29 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 10 a liquid crystal aligning agent D30 was prepared in the same manner as in Example 2, except that the liquid crystal aligning agent D12 obtained in Synthesis Example 24 was used instead of the liquid crystal aligning agent D1.
- the obtained liquid crystal aligning agent D30 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 11 a liquid crystal aligning agent D31 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D13 obtained in Synthesis Example 25 was used instead of the liquid crystal aligning agent D1.
- the obtained liquid crystal aligning agent D31 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 12 a liquid crystal aligning agent D32 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D14 obtained in Synthesis Example 26 was used instead of the liquid crystal aligning agent D1.
- the obtained liquid crystal aligning agent D32 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 13 a liquid crystal aligning agent D33 was prepared in the same manner as in Example 1 except that the polymerizable compound RM7 obtained in Synthesis Example 7 was used instead of the polymerizable compound RM1.
- the obtained liquid crystal aligning agent D33 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 14 a liquid crystal aligning agent D34 was prepared in the same manner as in Example 1 except that the polymerizable compound RM8 obtained in Synthesis Example 8 was used instead of the polymerizable compound RM1.
- the obtained liquid crystal aligning agent D34 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 1 a liquid crystal aligning agent D35 was prepared in the same manner as in Example 1 except that the polymerizable compound RM5 obtained in Synthesis Example 5 was used instead of the polymerizable compound RM1.
- the obtained liquid crystal aligning agent D35 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 2 a liquid crystal aligning agent D36 was prepared in the same manner as in Example 2 except that the polymerizable compound RM5 obtained in Synthesis Example 5 was used instead of the polymerizable compound RM1.
- the obtained liquid crystal aligning agent D36 was stored in a freezer at ⁇ 20 ° C. for 1 day, and left to stand at room temperature for 3 hours to thaw, and precipitates were confirmed.
- Example 3 a liquid crystal aligning agent D37 was prepared in the same manner as in Example 1 except that the polymerizable compound RM6 obtained in Synthesis Example 6 was used instead of the polymerizable compound RM1.
- the obtained liquid crystal aligning agent D37 was stored in a freezer at ⁇ 20 ° C. for 1 day, and allowed to stand at room temperature for 3 hours to thaw, and precipitates were confirmed.
- Example 2 a liquid crystal aligning agent D38 was prepared in the same manner as in Example 2, except that the polymerizable compound RM6 obtained in Synthesis Example 6 was used instead of the polymerizable compound RM1.
- the obtained liquid crystal aligning agent D38 was stored in a freezer at ⁇ 20 ° C. for 1 day, and allowed to stand at room temperature for 3 hours to thaw, and precipitates were confirmed.
- Example 5 a liquid crystal aligning agent D39 was prepared in the same manner as in Example 1 except that the polymerizable compound RM9 obtained in Synthesis Example 9 was used instead of the polymerizable compound RM1.
- the obtained liquid crystal aligning agent D39 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 6 a liquid crystal aligning agent D40 was prepared in the same manner as in Example 1 except that the polymerizable compound RM10 obtained in Synthesis Example 10 was used instead of the polymerizable compound RM1.
- the obtained liquid crystal aligning agent D40 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 15 ⁇ Production of liquid crystal cell> Using the liquid crystal aligning agent D15 obtained in Example 1, an SC-PVA liquid crystal cell was prepared according to the following procedure.
- the liquid crystal aligning agent D15 obtained in Example 1 was spin-coated on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 ⁇ m ⁇ 300 ⁇ m and a line / space of 5 ⁇ m was formed, and then heated at 80 ° C. After drying on a plate for 90 seconds, baking was performed in a hot air circulation oven at 200 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.
- Liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to produce a liquid crystal cell.
- the prepared liquid crystal cell was then placed in a 120 ° hot air circulation oven for 1 hour to realign the liquid crystal.
- the response speed of the obtained liquid crystal cell was measured by the following method. Thereafter, with a DC voltage of 15 V applied to the liquid crystal cell, UV was applied from the outside of the liquid crystal cell through a 365 nm bandpass filter at 10 J / cm 2 . Thereafter, the response speed was measured again, and the response speed before and after UV irradiation was compared. Further, the pretilt angle of the pixel portion of the cell after UV irradiation was measured.
- a liquid crystal cell was arranged between a pair of polarizing plates in a measuring apparatus configured in the order of a backlight, a pair of polarizing plates in a crossed Nicol state, and a light amount detector.
- the ITO electrode pattern in which the line / space was formed was at an angle of 45 ° with respect to the crossed Nicols.
- a rectangular wave with a voltage of ⁇ 6 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the change until the luminance observed by the light quantity detector is saturated is captured by an oscilloscope.
- the luminance when no voltage is applied is obtained.
- a voltage of 0% and ⁇ 4 V was applied, the saturated luminance value was set to 100%, and the time taken for the luminance to change from 10% to 90% was defined as the response speed.
- Example 16 to Example 28> instead of the liquid crystal aligning agent D15, the same operation as in Example 21 was performed except that the liquid crystal aligning agent described in Table 1 was used, and the response speed before and after UV irradiation was compared. The pretilt angle was measured. Moreover, the bright spot observation result in a liquid crystal cell was also performed.
- Example 29 To the liquid crystal aligning agent D10 (10.0 g) obtained in Synthesis Example 22, RM13 synthesized in Synthesis Example 27 was added at 0.06 g (10% by mass with respect to the solid content of the liquid crystal aligning agent D10)) at room temperature.
- the liquid crystal aligning agent D41 was prepared by stirring and dissolving for 3 hours. When the obtained liquid crystal aligning agent D41 was stored in a freezer at ⁇ 20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
- Example 30> The liquid crystal aligning agent D41 prepared in Example 29 was subjected to the same operation as in Example 15, and the response speed before and after UV irradiation was compared. The pretilt angle was measured and the bright spot in the liquid crystal cell was observed.
- Example 27 and Comparative Example 11 are different in F substitution (RM7) / No (RM9)
- Example 28 and Comparative Example 12 are Comparing the presence of F substitution (RM8) and absence (RM10)
- the solubility in liquid crystal is improved.
- Reference Example 9 and Reference Example 10 even when the terphenyl skeleton is rigid and less soluble than the biphenyl skeleton, the introduction of the halogen group improves the solubility of the polymerizable compound, and the liquid crystal aligning agent It can be confirmed that the storage stability is also improved.
- Reference Examples 7, 8, 11, and 12 high solubility of the polymerizable compound was confirmed.
- the halogen-substituted polymerizable compound improves the solubility of the polymerizable compound
- the liquid crystal aligning agent exhibits high storage stability, and further improves the solubility in the liquid crystal.
- a liquid crystal aligning agent to which a halogen-substituted polysynthetic compound is added can exhibit a tilt angle in a SC-PVA liquid crystal cell in the same manner as a liquid crystal aligning agent to which a non-halogen-substituted polymerizable compound is added. confirmed.
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Abstract
Description
このような垂直配向方式の液晶表示素子では、あらかじめ液晶組成物中に光重合性化合物を添加し、ポリイミド等の垂直配向膜と共に用いて、液晶セルに電圧を印加しながら紫外線を照射することで、液晶の応答速度を速くする技術(例えば、特許文献1及び非特許文献1参照)が知られている(PSA(Polymer sustained Alignment)型液晶ディスプレイ)。 In a liquid crystal display element of a method in which liquid crystal molecules aligned perpendicular to a substrate are responded by an electric field (also referred to as a vertical alignment (VA) method), an ultraviolet ray is applied while applying a voltage to the liquid crystal molecules in the manufacturing process. There is a thing including the process of irradiating.
In such a vertical alignment type liquid crystal display element, a photopolymerizable compound is added to a liquid crystal composition in advance and used together with a vertical alignment film such as polyimide to irradiate ultraviolet rays while applying a voltage to a liquid crystal cell. A technique for increasing the response speed of liquid crystal (for example, see Patent Document 1 and Non-Patent Document 1) is known (PSA (Polymer sustained Alignment) type liquid crystal display).
また、光重合性化合物を液晶組成物中ではなく液晶配向膜中に添加することによっても、液晶表示素子の応答速度が速くなることが報告されている(SC-PVA型液晶ディスプレイ)(例えば、非特許文献2参照)。
一方、添加光重合性化合物としてはある種の重合性モノマーが知られている(特許文献2~6)。 Usually, the direction in which the liquid crystal molecules tilt in response to an electric field is controlled by protrusions provided on the substrate or slits provided on the display electrode, but a liquid crystal composition is added with a photopolymerizable compound. By irradiating ultraviolet rays while applying voltage to the cell, a polymer structure in which the tilted direction of the liquid crystal molecules is memorized is formed on the liquid crystal alignment film. It is said that the response speed of the liquid crystal display element is faster than the control method.
It has also been reported that the response speed of the liquid crystal display element is increased by adding a photopolymerizable compound to the liquid crystal alignment film instead of the liquid crystal composition (SC-PVA liquid crystal display) (for example, Non-patent document 2).
On the other hand, as the added photopolymerizable compound, a certain polymerizable monomer is known (Patent Documents 2 to 6).
具体的には、本発明の目的は、液晶配向剤や液晶への溶解性を向上させた重合性化合物を提供することにある。 An object of the present invention is to solve the problems of the prior art described above.
Specifically, an object of the present invention is to provide a polymerizable compound having improved solubility in a liquid crystal aligning agent or liquid crystal.
1.ハロゲン原子で少なくとも一置換されているアリール基と、2個のα-メチレン-γ-ブチロラクトン基を有する重合性化合物。
2.下記の式[1]で表されることを特徴とする重合性化合物。 The present invention is based on such knowledge and has the following gist.
1. A polymerizable compound having an aryl group at least monosubstituted with a halogen atom and two α-methylene-γ-butyrolactone groups.
2. A polymerizable compound represented by the following formula [1].
3.式[1]中、Arは下記式[2]乃至[4]で表される構造からなる重合性化合物。(Xはハロゲン基を示し、特にフッ素基が好ましい。m1~m6は各々独立に0~4の整数であり、m7およびm8は各々独立に0~3の整数であり、m1+m2は1以上8以下であり、m3+m4+m5は1以上12以下であり、m6+m7+m8は1以上10以下である) In the formula [1], Ar is a divalent organic group containing an aromatic ring having at least one halogen substituent, and n1 and n2 are each independently an integer of 1 to 10.
3. In the formula [1], Ar is a polymerizable compound having a structure represented by the following formulas [2] to [4]. (X represents a halogen group, particularly preferably a fluorine group. M 1 to m 6 are each independently an integer of 0 to 4, m 7 and m 8 are each independently an integer of 0 to 3, and m 1 + M 2 is 1 or more and 8 or less, m 3 + m 4 + m 5 is 1 or more and 12 or less, and m 6 + m 7 + m 8 is 1 or more and 10 or less)
5.式[2]乃至[4]中、Xはフッ素基を示し、m1+m2は1以上3以下であり、m3+m4+m5は1以上4以下であり、m6+m7+m8は1以上3以下である上記4記載の化合物。
6.下記式[5]乃至[7]で表される化合物からなる群から選ばれる重合性化合物。(n1は1~10の整数である。) 4). 4. The polymerizable compound as described in any one of 1 to 3 above, wherein X represents a fluorine group.
5. In formulas [2] to [4], X represents a fluorine group, m 1 + m 2 is 1 or more and 3 or less, m 3 + m 4 + m 5 is 1 or more and 4 or less, and m 6 + m 7 + m 8 is 5. The compound according to 4 above, which is 1 or more and 3 or less.
6). A polymerizable compound selected from the group consisting of compounds represented by the following formulas [5] to [7]. (n1 is an integer of 1 to 10)
8.上記1~7のいずれかに記載の重合性化合物と、ポリイミド及びポリイミド前駆体から選ばれる少なくとも一種の重合体とを含有する液晶配向剤。 7-1. A polymerizable compound represented by the above formula [1-6].
8). A liquid crystal aligning agent comprising the polymerizable compound according to any one of 1 to 7 above and at least one polymer selected from polyimide and a polyimide precursor.
<重合性化合物>
本発明の重合性化合物は、下記の式[1]で表される。 Hereinafter, the present invention will be described in more detail.
<Polymerizable compound>
The polymerizable compound of the present invention is represented by the following formula [1].
合成のしやすさから、n1とn2は同じであることが好ましい。
Arとしては、下記式[2]乃至[4]で表されるものが好ましい。 In the formula [1], Ar is a divalent organic group containing an aromatic ring having at least one halogen substituent, and n 1 and n 2 are each independently an integer of 1 to 10.
From the viewpoint of ease of synthesis, n1 and n2 are preferably the same.
Ar is preferably represented by the following formulas [2] to [4].
式[2]乃至[4]において、Xはフッ素基を示し、m1+m2は1以上3以下であり、m3+m4+m5は1以上4以下であり、m6+m7+m8は1以上3以下であるのが、合成のしやすさや経済性などから好ましい。いずれも、特に、1以上2以下であるのが好ましい。また、溶解性の点から、Xの置換位置は、Arが非対称になるような置換位置であることが好ましい。 In the formula, X represents a halogen group, and a fluorine group is particularly preferable. m 1 to m 6 are each independently an integer of 0 to 4, m 7 and m 8 are each independently an integer of 0 to 3, m 1 + m 2 is from 1 to 8, and m 3 + m 4 + M 5 is 1 or more and 12 or less, and m 6 + m 7 + m 8 is 1 or more and 10 or less.
In the formulas [2] to [4], X represents a fluorine group, m 1 + m 2 is 1 or more and 3 or less, m 3 + m 4 + m 5 is 1 or more and 4 or less, and m 6 + m 7 + m 8 is It is preferably 1 or more and 3 or less from the viewpoint of easiness of synthesis and economic efficiency. In any case, it is particularly preferably 1 or more and 2 or less. From the viewpoint of solubility, the substitution position of X is preferably such that Ar is asymmetric.
F含有ビアリール化合物[4-A]としては、以下のビフェニル化合物[4-1]~[4-42]、及び、フェニルナフチル化合物[4-43]~[4-58]が挙げられる。 <Cross coupling reaction, F-containing biaryl compound>
Examples of the F-containing biaryl compound [4-A] include the following biphenyl compounds [4-1] to [4-42] and phenylnaphthyl compounds [4-43] to [4-58].
以下、[反応式1]のカップリング反応によって得られるF含有ターフェニル化合物[4-B]としては、以下の化合物が挙げられる。F含有ターフェニル化合物[4-B]は、3環構造中真中のベンゼン環(B)に対して左右のベンゼン環(A)が同じ構造である。 <Cross coupling reaction, F-containing terphenyl compound>
Hereinafter, examples of the F-containing terphenyl compound [4-B] obtained by the coupling reaction of [Reaction Formula 1] include the following compounds. The F-containing terphenyl compound [4-B] has a structure in which the left and right benzene rings (A) are the same as the middle benzene ring (B) in the tricyclic structure.
F含有エーテル化合物[9]は、下記に示すように、フェノール性水酸基を含有する芳香族化合物[4-A]~[4-C]とハロゲン化アルキル[8]を塩基存在下、必要に応じて添加剤の存在下で反応させることにより得ることができる。 <F-containing etherification reaction>
As shown below, the F-containing ether compound [9] comprises an aromatic compound [4-A] to [4-C] containing a phenolic hydroxyl group and an alkyl halide [8] in the presence of a base as necessary. It can be obtained by reacting in the presence of an additive.
α-メチレン-γ-ブチロラクトン化合物[1]は、有機合成化学における手法を組み合わせることによって合成することができ、その合成法は特に限定されない。下記に示すように、アルデヒド又はケトン、アセタール、ケタールと金属試薬、アクリル酸誘導体を酸性条件下で反応させることにより合成することができる(参考文献:例えばP.Talaga,M.Schaeffer,C.Benezra and J.L.Stampf,Synthesis,530(1990))。 <Lactone ring synthesis reaction>
The α-methylene-γ-butyrolactone compound [1] can be synthesized by combining methods in organic synthetic chemistry, and the synthesis method is not particularly limited. As shown below, it can be synthesized by reacting an aldehyde or ketone, acetal, ketal with a metal reagent and an acrylic acid derivative under acidic conditions (reference: for example, P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530 (1990)).
本願は、液晶配向剤や液晶への溶解性を向上させた重合性化合物を含有する液晶配向剤をも提供する。本願の液晶配向剤は、[I]前記式[1]で表される化合物からなる群から選ばれる少なくとも1種の重合性化合物及び[II]ポリイミド及びポリイミド前駆体から選ばれる少なくとも1つの重合体を含有する。 <Liquid crystal aligning agent>
The present application also provides a liquid crystal aligning agent containing a polymerizable compound having improved solubility in a liquid crystal aligning agent or liquid crystal. The liquid crystal aligning agent of the present application is [I] at least one polymerizable compound selected from the group consisting of compounds represented by the formula [1], and [II] at least one polymer selected from polyimide and a polyimide precursor. Containing.
[II]ポリイミド及びポリイミド前駆体から選ばれる少なくとも1つの重合体としては、液晶配向剤に用いられる従来公知又は将来公知となり得るポリイミドやポリイミド前駆体を用いることができる。 <[II] At least one polymer selected from polyimide and polyimide precursor>
[II] As at least one polymer selected from a polyimide and a polyimide precursor, a polyimide or a polyimide precursor that can be conventionally known or used in the future for a liquid crystal aligning agent can be used.
<<(I)液晶を垂直に配向させる側鎖>>
(I)液晶を垂直に配向させる側鎖(以下、側鎖Aともいう)とは、液晶分子を基板に対して垂直に配向させる能力を有する側鎖であり、この能力を有していればその構造は限定されない。このような側鎖としては、例えば、長鎖のアルキル基やフルオロアルキル基、末端にアルキル基やフルオロアルキル基を有する環状基、ステロイド基などが知られており、本発明においても好適に用いられる。これらの基は、上記の能力を有している限りにおいて、ポリイミド又はポリイミド前駆体の主鎖に直接結合していてもよく、適当な結合基を介して結合していてもよい。 [II] At least one polymer selected from polyimides and polyimide precursors may have (I) a side chain for vertically aligning liquid crystals for PSA type liquid crystal displays.
<< (I) Side chain for vertically aligning liquid crystal >>
(I) A side chain that aligns liquid crystal vertically (hereinafter also referred to as side chain A) is a side chain that has the ability to align liquid crystal molecules vertically with respect to the substrate. Its structure is not limited. As such a side chain, for example, a long-chain alkyl group or a fluoroalkyl group, a cyclic group having an alkyl group or a fluoroalkyl group at the terminal, a steroid group, or the like is known, and is preferably used in the present invention. . These groups may be directly bonded to the main chain of the polyimide or polyimide precursor as long as they have the above-mentioned ability, or may be bonded via an appropriate bonding group.
なお、式(a)中、l、m及びnはそれぞれ独立に0又は1の整数を表し、R1は炭素原子数2から6のアルキレン基、-O-、-COO-、-OCO-、-NHCO-、-CONH-、又は炭素原子数1から3のアルキレン-エーテル基を表し、R2、R3及びR4はそれぞれ独立にフェニレン基又はシクロアルキレン基を表し、R5は水素原子、炭素原子数2から24のアルキル基又はフッ素含有アルキル基、芳香環、脂肪族環、複素環、又はそれらからなる大環状置換体を表す。 Examples of the side chain A include those represented by the following formula (a).
In the formula (a), l, m and n each independently represents an integer of 0 or 1, and R 1 represents an alkylene group having 2 to 6 carbon atoms, —O—, —COO—, —OCO—, —NHCO—, —CONH—, or an alkylene-ether group having 1 to 3 carbon atoms, R 2 , R 3 and R 4 each independently represents a phenylene group or a cycloalkylene group, R 5 represents a hydrogen atom, It represents an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a macrocyclic substituent composed thereof.
また、l、m、nがともに0である場合、R5の構造として好ましくは炭素原子数12から22のアルキル基またはフッ素含有アルキル基、芳香環、脂肪族環、複素環、又はそれらからなる大環状置換体であり、より好ましくは炭素原子数12から20のアルキル基またはフッ素含有アルキル基である。 R 5 in the formula (a) represents a hydrogen atom, an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a macrocyclic substituent composed thereof. When at least one of l, m and n is 1, the structure of R 5 is preferably a hydrogen atom, an alkyl group having 2 to 14 carbon atoms or a fluorine-containing alkyl group, more preferably a hydrogen atom or carbon atom number. 2 to 12 alkyl groups or fluorine-containing alkyl groups.
When l, m, and n are all 0, the structure of R 5 is preferably an alkyl group having 12 to 22 carbon atoms, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or the like. A macrocyclic substituent, more preferably an alkyl group having 12 to 20 carbon atoms or a fluorine-containing alkyl group.
光反応性の側鎖(以下、側鎖Bともいう)とは、紫外線の照射によって反応し、共有結合を形成し得る官能基(以下、光架橋基とも言う)を有する架橋性側鎖、または、紫外線照射によりラジカルが発生する官能基を有する光ラジカル発生側鎖であり、この能力を有していればその構造は限定されない。
このような側鎖のうち、例えば光架橋基としてビニル基、アクリル基、メタクリル基、アントラセニル基、シンナモイル基、カルコニル基、クマリン基、マレイミド基、スチルベン基などを含有する側鎖などが知られており、本発明においても好適に用いられる。また、紫外線照射によりラジカルを発生する特定構造も好適に用いられる。これらの基は、上記の能力を有している限りにおいて、ポリイミド又はポリイミド前駆体の主鎖に直接結合していてもよく、適当な結合基を介して結合していてもよい。 <(II) Photoreactive side chain>
A photoreactive side chain (hereinafter also referred to as side chain B) is a crosslinkable side chain having a functional group (hereinafter also referred to as photocrosslinking group) that can react by irradiation with ultraviolet rays to form a covalent bond, or A photoradical generating side chain having a functional group capable of generating radicals upon irradiation with ultraviolet rays, and its structure is not limited as long as it has this ability.
Among such side chains, for example, a side chain containing a vinyl group, an acrylic group, a methacryl group, an anthracenyl group, a cinnamoyl group, a chalcone group, a coumarin group, a maleimide group, a stilbene group or the like as a photocrosslinking group is known. And is also preferably used in the present invention. In addition, a specific structure that generates radicals by ultraviolet irradiation is also preferably used. These groups may be directly bonded to the main chain of the polyimide or polyimide precursor as long as they have the above-mentioned ability, or may be bonded via an appropriate bonding group.
式(b-1)中、R6は-CH2-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH2O-、-N(CH3)-、-CON(CH3)-、-N(CH3)CO-、のいずれかを表し、R7は環状、非置換またはフッ素原子によって置換されている炭素数1から炭素数20のアルキレンを表し、ここでアルキレンの任意の-CH2-は-CF2-又は-CH=CH-で置き換えられていてもよく、次に挙げるいずれかの基が互いに隣り合わない場合において、これらの基に置き換えられていてもよい;-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、炭素環、複素環。R8は-CH2-、-O-、-COO-、-OCO-、-NHCO-、-NH-、-N(CH3)-、-CON(CH3)-、-N(CH3)CO-、炭素環、もしくは複素環のいずれかを表し、R9はスチリル基、-CR10=CH2基、炭素環、複素環又は以下の式R9-1~R9-31で表される構造を表し、R10は水素原子又はフッ素原子で置換されていてもよいメチル基を表す。 Examples of the side chain B include those represented by the following formulas (b-1) to (b-3).
In the formula (b-1), R 6 represents —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ) —, —CON (CH 3 ) —, —N (CH 3 ) CO—, wherein R 7 is cyclic, unsubstituted or substituted with a fluorine atom having 1 to 20 carbon atoms Represents alkylene, wherein any —CH 2 — in the alkylene may be replaced by —CF 2 — or —CH═CH—, and when any of the following groups are not adjacent to each other: May be replaced by a group; —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, carbocycle, heterocycle. R 8 represents —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —NH—, —N (CH 3 ) —, —CON (CH 3 ) —, —N (CH 3 ). CO—, a carbocycle, or a heterocycle, R 9 is a styryl group, —CR 10 ═CH 2 group, a carbocycle, a heterocycle, or a structure represented by the following formulas R9-1 to R9-31 R 10 represents a hydrogen atom or a methyl group which may be substituted with a fluorine atom.
式(b-2)で表される側鎖の具体例は、例えば以下のような構造が挙げられる(式中、Rは水素原子を表すか、フッ素で置換されていてもよいメチル基を表す)。 The side chain represented by the formula (b-2) is a side chain having a cinnamoyl structure and a methacrylic structure at the same time. In the formula (b-2), R 10 represents a group selected from —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, and —CO—. R 11 is an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are , May be replaced by a fluorine atom or an organic group. In addition, R 11 may be substituted with —CH 2 — when any of the following groups are not adjacent to each other; —O—, —NHCO—, —CONH—, — COO—, —OCO—, —NH—, —NHCONH—, —CO—. R 12 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—, or a single bond. R 13 represents a photocrosslinkable group such as a cinnamoyl group, a chalcone group, or a coumarin group. R 14 is a single bond, or an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more of the alkylene group, divalent carbocycle or heterocycle The hydrogen atom may be replaced with a fluorine atom or an organic group. In addition, R 14 may be substituted with —CH 2 — when any of the following groups are not adjacent to each other: —O—, —NHCO—, —CONH—, — COO—, —OCO—, —NH—, —NHCONH—, —CO—. R 15 represents a photopolymerizable group selected from either an acryl group or a methacryl group.
Specific examples of the side chain represented by the formula (b-2) include the following structures (in the formula, R represents a hydrogen atom or a methyl group which may be substituted with fluorine). ).
式(b-3)で表される側鎖の具体例は、例えば以下のような構造が挙げられる。 In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 3 represents —CH 2 —, —NR—, —O—, —S—.
Specific examples of the side chain represented by the formula (b-3) include the following structures.
側鎖Aを有するポリイミド前駆体の一種であるポリアミック酸は、原料であるジアミン及びテトラカルボン酸無水物のうち、いずれかが側鎖Aを有するか、双方が側鎖Aを有することにより、該原料を反応させることによって得ることができる。このうち、原料合成の容易性などから、側鎖Aを有するジアミン化合物を用いる方法が好ましい。
側鎖A及び側鎖Bを有するポリアミック酸は、原料であるジアミン及びテトラカルボン酸無水物のうち、いずれか一方のみが側鎖A及び側鎖Bを有するか、いずれか一方が側鎖Aのみを有し且つ他方が側鎖Bのみを有するか、いずれか一方が側鎖A及び側鎖Bを有し且つ他方が側鎖Aを有するか、いずれか一方が側鎖A及び側鎖Bを有し且つ他方が側鎖Bを有するか、又は、双方が側鎖A及び側鎖Bを有することにより、該原料を反応させることによって得ることができる。このうち、原料合成の容易性などから、側鎖Aを有するジアミン化合物、側鎖Bを有するジアミン化合物、及び、側鎖A又は側鎖Bを有しないテトラカルボン酸を用いる方法が好ましい。
以下、側鎖Aを有するジアミン化合物について説明し、次いで、側鎖Bを有するジアミン化合物について説明する。 <Polyamic acid>
A polyamic acid which is a kind of polyimide precursor having a side chain A is either a side chain A or a side chain A among diamine and tetracarboxylic anhydride as raw materials, It can be obtained by reacting raw materials. Among these, the method using a diamine compound having a side chain A is preferable from the viewpoint of ease of raw material synthesis.
The polyamic acid having a side chain A and a side chain B is either a side chain A or a side chain B, or only one side chain A is a raw material of diamine and tetracarboxylic anhydride. And the other has only the side chain B, either one has the side chain A and the side chain B and the other has the side chain A, either one has the side chain A and the side chain B And the other has side chain B, or both have side chain A and side chain B, and can be obtained by reacting the raw materials. Among these, the method using a diamine compound having a side chain A, a diamine compound having a side chain B, and a tetracarboxylic acid having no side chain A or side chain B is preferable from the viewpoint of ease of raw material synthesis.
Hereinafter, the diamine compound having the side chain A will be described, and then the diamine compound having the side chain B will be described.
側鎖Aを有するジアミン化合物(以下、ジアミンAとも言う)としては、ジアミン側鎖にアルキル基、フッ素含有アルキル基、芳香環、脂肪族環、複素環、又はそれらからなる大環状置換体を有するジアミンを例として挙げることができる。具体的には、前記式(a)で表される側鎖を有するジアミンを挙げることができる。より具体的には例えば下記式(1)、(3)、(4)、(5)で表されるジアミンを挙げることができるが、これに限定されるものではない。なお、式(1)中のl、m、n、R1~R5の定義については、前記式(a)と同じである。 <Diamine compound having side chain A>
As a diamine compound having a side chain A (hereinafter also referred to as diamine A), the diamine side chain has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a macrocyclic substituent composed thereof. A diamine can be mentioned as an example. Specific examples include diamines having a side chain represented by the formula (a). More specifically, examples include diamines represented by the following formulas (1), (3), (4), and (5), but are not limited thereto. The definitions of l, m, n and R 1 to R 5 in the formula (1) are the same as those in the formula (a).
式[A-6]及び式[A-7]中、A2は各々独立に、-O-、-OCH2-、-CH2O-、-COOCH2-、又は-CH2OCO-を示し、A3は各々独立に、炭素数1以上22以下のアルキル基、アルコキシ基、フッ素含有アルキル基又はフッ素含有アルコキシ基である。
式[A-8]~式[A-10]中、A4は各々独立に、-COO-、-OCO-、-CONH-、-NHCO-、-COOCH2-、-CH2OCO-、-CH2O-、-OCH2-、又は-CH2-を示し、A5は各々独立に、炭素数1以上22以下のアルキル基、アルコキシ基、フッ素含有アルキル基又はフッ素含有アルコキシ基である。 In the formulas [A-1] to [A-5], A 1 each independently represents an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group.
In formula [A-6] and [A-7], A 2 each independently represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—. , A 3 are each independently an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.
In formulas [A-8] to [A-10], A 4 each independently represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, — CH 2 O -, - OCH 2 -, or -CH 2 - indicates, a 5 are each independently 1 to 22 alkyl group carbon atoms, an alkoxy group, a fluorine-containing alkyl group or fluorine-containing alkoxy group.
式[A-13]及び式[A-14]中、A8は各々独立に、炭素数3以上12以下のアルキル基であり、1,4-シクロヘキシレンのシス-トランス異性は、それぞれトランス異性体である。
式[A-15]及び式[A-16]中、A9は各々独立に、炭素数3以上12以下のアルキル基であり、1,4-シクロヘキシレンのシス-トランス異性は、それぞれトランス異性体である。 In Formula [A-11] and Formula [A-12], A 6 each independently represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, — CH 2 O—, —OCH 2 —, —CH 2 —, —O—, or —NH—, and A 7 represents a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group , An acetoxy group, or a hydroxyl group.
In formulas [A-13] and [A-14], A 8 each independently represents an alkyl group having 3 to 12 carbon atoms, and cis-trans isomerism of 1,4-cyclohexylene is trans isomerism, respectively. Is the body.
In formula [A-15] and formula [A-16], A 9 is each independently an alkyl group having 3 to 12 carbon atoms, and cis-trans isomerism of 1,4-cyclohexylene is trans isomerism, respectively. Is the body.
上記のジアミン化合物は、液晶配向膜とした際の液晶配向性、プレチルト角、電圧保持特性、蓄積電荷などの特性に応じて、1種類または2種類以上を混合して使用することもできる。 Of these, [A-1], [A-2], [A-3], [A-7], [A-14], [A-14], [A-14], [A-14], [A-14], [A-14], [A-14], [A-14] The diamines of A-16], [A-21] and [A-22] are preferred.
The diamine compounds can be used alone or in combination of two or more depending on the liquid crystal alignment properties, pretilt angle, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.
側鎖Bを有するジアミン化合物(以下、ジアミンBとも言う)の例として、ジアミン側鎖にビニル基、アクリル基、メタクリル基、アントラセニル基、シンナモイル基、カルコニル基、クマリン基、マレイミド基、スチルベン基などの光架橋基を有するジアミンや、紫外線照射によりラジカルを発生する特定構造を有するジアミンを挙げることができる。具体的には、前記式(b-1)~(b-3)で表される側鎖を有するジアミンを挙げることができる。具体例として下記の一般式(2)(式(2)中のR6、R7、R8、R9及びR10の定義は前記式(b-1)と同じである)で表されるジアミンを挙げることができるが、これに限定されるものではない。 <Diamine compound having side chain B>
Examples of diamine compounds having side chain B (hereinafter also referred to as diamine B) include vinyl group, acrylic group, methacryl group, anthracenyl group, cinnamoyl group, chalconyl group, coumarin group, maleimide group, stilbene group, etc. And a diamine having a specific structure capable of generating radicals upon irradiation with ultraviolet rays. Specific examples include diamines having side chains represented by the formulas (b-1) to (b-3). As a specific example, it is represented by the following general formula (2) (the definitions of R 6 , R 7 , R 8 , R 9 and R 10 in formula (2) are the same as those in formula (b-1)). Although a diamine can be mentioned, it is not limited to this.
具体的には以下のような化合物が挙げられるが、これに限定されるものではない。 The bonding position of the two amino groups (—NH 2 ) in the formula (2) is not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine compound, the positions 2, 4 or 3, 5 are more preferable.
Specific examples include the following compounds, but are not limited thereto.
上記のジアミン化合物は、液晶配向膜とした際の液晶配向性、プレチルト角、電圧保持特性、蓄積電荷などの特性、液晶表示素子とした際の液晶の応答速度などに応じて、1種類または2種類以上を混合して使用することもできる。 In the formula, X independently represents a linking group selected from —C—, —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, and l, m, n, Each independently represents an integer of 0 to 20, k represents an integer of 1 to 20, and R represents a hydrogen atom or a methyl group.
The diamine compound may be one kind or two depending on the liquid crystal orientation, the pretilt angle, the voltage holding characteristics, the accumulated charge characteristics, and the liquid crystal response speed when the liquid crystal display element is used. A mixture of more than one can also be used.
本発明に用いられるポリアミック酸は、本発明の効果を損わない限りにおいて、ジアミンA及びジアミンB以外のその他のジアミン化合物をジアミン成分として併用することができる。その具体例を以下に挙げる。 <Other diamine compounds>
The polyamic acid used in the present invention can be used in combination with other diamine compounds other than diamine A and diamine B as the diamine component as long as the effects of the present invention are not impaired. Specific examples are given below.
本発明に用いるポリアミック酸の合成において、上記のジアミン成分と反応させるテトラカルボン酸二無水物は特に限定されない。その具体例を以下に挙げる。 <Tetracarboxylic dianhydride>
In the synthesis of the polyamic acid used in the present invention, the tetracarboxylic dianhydride to be reacted with the diamine component is not particularly limited. Specific examples are given below.
ジアミン成分とテトラカルボン酸二無水物との反応により、ポリアミック酸を得るにあたっては、公知の合成手法を用いることができる。一般的には、ジアミン成分とテトラカルボン酸二無水物とを有機溶媒中で反応させる方法である。ジアミン成分とテトラカルボン酸二無水物との反応は、有機溶媒中で比較的容易に進行し、かつ副生成物が発生しない点で有利である。 <Synthesis of polyamic acid>
In obtaining a polyamic acid by a reaction between a diamine component and tetracarboxylic dianhydride, a known synthesis method can be used. In general, the diamine component and tetracarboxylic dianhydride are reacted in an organic solvent. The reaction between the diamine component and tetracarboxylic dianhydride is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.
以下に、有機溶媒の具体例を挙げる。 The organic solvent used in the above reaction is not particularly limited as long as the produced polyamic acid dissolves. Furthermore, even if it is an organic solvent which does not dissolve a polyamic acid, it may be mixed with the said solvent and used as long as the produced polyamic acid does not precipitate. In addition, since the water | moisture content in an organic solvent inhibits a polymerization reaction and also causes the produced polyamic acid to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent.
Specific examples of the organic solvent are given below.
上記したポリアミック酸をイミド化させてポリイミドとする方法としては、ポリアミック酸の溶液をそのまま加熱する熱イミド化、ポリアミック酸の溶液に触媒を添加する触媒イミド化が挙げられる。
本発明に用いるポリイミドにおいて、ポリアミック酸からポリイミドへのイミド化率は、必ずしも100%である必要はない。 <Polyimide>
Examples of the method for imidizing the polyamic acid to form a polyimide include thermal imidization in which a polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.
In the polyimide used in the present invention, the imidization ratio from polyamic acid to polyimide is not necessarily 100%.
本発明の液晶配向剤は、上記[I]重合性化合物;及び上記[II]ポリイミド及びポリイミド前駆体から選ばれる少なくとも一種の重合体;を有するが、該[I]及び[II]成分以外に、樹脂被膜を形成するための樹脂成分を有してもよい。全樹脂成分の含有量は、液晶配向剤100質量%中、1質量%~20質量%、好ましくは3質量%~15質量%、より好ましくは3~10質量%であるのがよい。 <Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention has the above [I] polymerizable compound; and the above [II] at least one polymer selected from polyimides and polyimide precursors, in addition to the [I] and [II] components. The resin component for forming a resin film may be included. The content of all the resin components is 1% by mass to 20% by mass, preferably 3% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass in 100% by mass of the liquid crystal aligning agent.
かかる他の重合体として、例えば、側鎖Bを有さないポリイミド又はポリイミド前駆体、側鎖Aと側鎖Bとを同時に有さないポリイミド又はポリイミド前駆体などを挙げることができるが、これらに限定されない。 In the liquid crystal aligning agent used in the present invention, all of the above resin components may be polyimide or polyimide precursor having side chain A, or polyimide or polyimide precursor having side chain A and side chain B. A mixture of these may be used, and other polymers may be further mixed. In that case, the content of the other polymer in the resin component is preferably 0.5% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass.
Examples of such other polymers include polyimide or polyimide precursor having no side chain B, polyimide or polyimide precursor not having side chain A and side chain B at the same time. It is not limited.
本発明の液晶配向剤に用いる有機溶媒は、上述した樹脂成分を溶解させる有機溶媒であれば特に限定されない。この有機溶媒は1種類の溶媒であっても2種類以上の混合溶媒であってもよい。あえて有機溶媒の具体例を挙げるならば、前記のポリアミック酸合成で例示した有機溶媒を挙げることができる。中でもN-メチル-2-ピロリドン、γ-ブチロラクトン、N-エチル-2-ピロリドン、1,3-ジメチル-2-イミダゾリジノン、3-メトキシ-N,N-ジメチルプロパンアミドは、樹脂成分の溶解性の観点から好ましい。 <Solvent>
The organic solvent used for the liquid crystal aligning agent of this invention will not be specifically limited if it is an organic solvent in which the resin component mentioned above is dissolved. This organic solvent may be one type of solvent or a mixed solvent of two or more types. If the specific example of an organic solvent is given dare, the organic solvent illustrated by the said polyamic acid synthesis can be mentioned. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 3-methoxy-N, N-dimethylpropanamide dissolve resin components. From the viewpoint of sex.
例えば、イソプロピルアルコール、メトキシメチルペンタノール、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルセロソルブアセテート、ブチルセロソルブアセテート、エチルセロソルブアセテート、ブチルカルビトール、エチルカルビトール、エチルカルビトールアセテート、エチレングリコール、エチレングリコールモノアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコール、プロピレングリコールモノアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコール-tert-ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノアセテート、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジプロピレングリコールモノアセテートモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノアセテートモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノアセテートモノプロピルエーテル、3-メチル-3-メトキシブチルアセテート、トリプロピレングリコールメチルエーテル、3-メチル-3-メトキシブタノール、ジイソプロピルエーテル、エチルイソブチルエーテル、ジイソブチレン、アミルアセテート、ブチルブチレート、ブチルエーテル、ジイソブチルケトン、メチルシクロへキセン、プロピルエーテル、ジヘキシルエーテル、n-へキサン、n-ペンタン、n-オクタン、ジエチルエーテル、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸n-ブチル、酢酸プロピレングリコールモノエチルエーテル、ピルビン酸メチル、ピルビン酸エチル、3-メトキシプロピオン酸メチル、3-エトキシプロピオン酸メチルエチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸、3-メトキシプロピオン酸、3-メトキシプロピオン酸プロピル、3-メトキシプロピオン酸ブチル、1-メトキシ-2-プロパノール、1-エトキシ-2-プロパノール、1-ブトキシ-2-プロパノール、1-フェノキシ-2-プロパノール、プロピレングリコールモノアセテート、プロピレングリコールジアセテート、プロピレングリコール-1-モノメチルエーテル-2-アセテート、プロピレングリコール-1-モノエチルエーテル-2-アセテート、ジプロピレングリコール、2-(2-エトキシプロポキシ)プロパノール、乳酸メチルエステル、乳酸エチルエステル、乳酸n-プロピルエステル、乳酸n-ブチルエステル、乳酸イソアミルエステル、2-エチル-1-ヘキサノールなどが挙げられる。これらの溶媒は複数種類を混合してもよい。これらの溶媒を用いる場合は、液晶配向剤に含まれる溶媒全体の5~80質量%であることが好ましく、より好ましくは20~60質量%である。 Moreover, since the solvent as shown below improves the uniformity and smoothness of the coating film, it is preferable to use the solvent by mixing it with a solvent having high solubility of the resin component.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, Ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol Cole monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol Monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate , Butyl butyrate Butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene acetate Glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxy Propyl propionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol Monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, methyl lactate Examples thereof include esters, lactate ethyl esters, lactate n-propyl esters, lactate n-butyl esters, lactyl isoamyl esters, and 2-ethyl-1-hexanol. A plurality of these solvents may be mixed. When these solvents are used, the content is preferably 5 to 80% by mass, more preferably 20 to 60% by mass based on the total amount of the solvent contained in the liquid crystal aligning agent.
本発明に用いられる液晶配向剤には、上記の他、本発明の効果が損なわれない範囲であれば、液晶配向膜の誘電率や導電性などの電気特性を変化させる目的の誘電体や導電物質を添加してもよい。 Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include a functional silane-containing compound and an epoxy group-containing compound. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-tri Toxisilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxy Silane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyl Trimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Lopylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl -2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′ , N ′,-tetraglycidyl-4, 4′-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, etc. It is done. In order to further increase the rubbing resistance of the resin using the present invention, a phenol compound such as 2,2′-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane or tetra (methoxymethyl) bisphenol is added. Also good. When these compounds are used, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.
In addition to the above, the liquid crystal aligning agent used in the present invention is a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired. Substances may be added.
例えば、本発明の液晶配向剤を、基板に塗布した後、必要に応じて乾燥し、焼成を行うことで得られる硬化膜を、そのまま液晶配向膜として用いることもできる。また、この硬化膜をラビングしたり、偏光又は特定の波長の光等を照射したり、イオンビーム等の処理をしたり、SC-PVA用配向膜として液晶充填後の液晶表示素子に電圧を印加した状態でUVを照射することも可能である。 <Liquid crystal alignment film>
For example, after apply | coating the liquid crystal aligning agent of this invention to a board | substrate, after drying as needed, the cured film obtained by baking can also be used as a liquid crystal aligning film as it is. In addition, this cured film is rubbed, irradiated with polarized light or light of a specific wavelength, treated with an ion beam, etc., and a voltage is applied to the liquid crystal display element after filling the liquid crystal as an alignment film for SC-PVA. It is also possible to irradiate UV in such a state.
本発明の液晶表示素子は、上記の方法により、基板に液晶配向膜を形成した後、公知の方法で液晶セルを作製して得ることができる。液晶表示素子の具体例としては、対向するように配置された2枚の基板と、基板間に設けられた液晶層と、基板と液晶層との間に設けられ本発明の液晶配向剤により形成された上記液晶配向膜とを有する液晶セルを具備する垂直配向方式の液晶表示素子である。具体的には、本発明の液晶配向剤を2枚の基板上に塗布して焼成することにより液晶配向膜を形成し、この液晶配向膜が対向するように2枚の基板を配置し、この2枚の基板の間に液晶で構成された液晶層を挟持し、すなわち、液晶配向膜に接触させて液晶層を設け、液晶配向膜及び液晶層に電圧を印加しながら紫外線を照射することで作製される液晶セルを具備する垂直配向方式の液晶表示素子である。このように本発明の液晶配向剤により形成された液晶配向膜を用い、液晶配向膜及び液晶層に電圧を印加しながら紫外線を照射して、重合性化合物を重合させると共に、重合体が有する光反応性の側鎖同士や、重合体が有する光反応性の側鎖と重合性化合物を反応させることにより、より効率的に液晶の配向が固定化され、応答速度が顕著に優れた液晶表示素子となる。 <Liquid crystal display element having liquid crystal alignment film>
The liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method and then preparing a liquid crystal cell by a known method. Specific examples of the liquid crystal display element include two substrates disposed so as to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal aligning agent provided between the substrate and the liquid crystal layer. A vertical alignment type liquid crystal display device comprising a liquid crystal cell having the above-described liquid crystal alignment film. Specifically, the liquid crystal aligning agent of the present invention is applied onto two substrates and baked to form a liquid crystal aligning film, and the two substrates are arranged so that the liquid crystal aligning films face each other. A liquid crystal layer composed of liquid crystal is sandwiched between two substrates, that is, a liquid crystal layer is provided in contact with the liquid crystal alignment film, and ultraviolet rays are applied while applying a voltage to the liquid crystal alignment film and the liquid crystal layer. This is a vertical alignment type liquid crystal display device including a liquid crystal cell to be manufactured. As described above, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is used to irradiate ultraviolet rays while applying voltage to the liquid crystal alignment film and the liquid crystal layer to polymerize the polymerizable compound, and the light possessed by the polymer. A liquid crystal display device in which the alignment of the liquid crystal is more efficiently fixed and the response speed is remarkably improved by reacting the reactive side chains or the photoreactive side chain of the polymer with the polymerizable compound. It becomes.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されない。 The liquid crystal aligning agent is not only useful as a liquid crystal aligning agent for producing a vertical alignment type liquid crystal display element such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display, but also by a rubbing process or a photo-alignment process. It can also be suitably used for applications of the liquid crystal alignment film to be produced.
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
(酸二無水物)
BODA:ビシクロ[3,3,0]オクタン-2,4,6,8-テトラカルボン酸二無水物。
CBDA:1,2,3,4-シクロブタンテトラカルボン酸二無水物。
PMDA:ピロメリット酸二無水物
TCA:2,3,5-トリカルボキシシクロペンチル酢酸-1,4,2,3-二無水物
(ジアミン) The abbreviations used in the preparation of the following liquid crystal aligning agents are as follows.
(Acid dianhydride)
BODA: Bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride.
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride.
PMDA: pyromellitic dianhydride TCA: 2,3,5-tricarboxycyclopentylacetic acid-1,4,2,3-dianhydride (diamine)
下記式DA-2で表される垂直配向性ジアミンは、特許第4466373号に記載される方法で合成した。
下記式DA-3で表される垂直配向性ジアミンは、特許第5273035号に記載される方法で合成した。
下記式DA-4で表される垂直配向性ジアミンは、東京化成工業株式会社製のものを購入した。
下記式DA-5で表される垂直配向性ジアミンは、WO2009/093704に記載の方法で合成した。
下記式DA-6で表される光反応性ジアミンは、以下のように調製した。
下記式DA-7で表されるジアミンは、和光純薬工業株式会社製のものを購入した。
下記式DA-8で表されるラジカル発生ジアミンは、以下のように調製した。
下記式DA-9で表されるジアミンは、後述の「(原料合成例3)DA-9の合成」で記載する方法により調製した。 A vertically oriented diamine represented by the following formula DA-1 was synthesized by the method described in Japanese Patent No. 4085206.
A vertically oriented diamine represented by the following formula DA-2 was synthesized by the method described in Japanese Patent No. 4466373.
A vertically-aligned diamine represented by the following formula DA-3 was synthesized by the method described in Japanese Patent No. 5273035.
The vertically oriented diamine represented by the following formula DA-4 was purchased from Tokyo Chemical Industry Co., Ltd.
A vertically oriented diamine represented by the following formula DA-5 was synthesized by the method described in WO2009 / 093704.
A photoreactive diamine represented by the following formula DA-6 was prepared as follows.
The diamine represented by the following formula DA-7 was purchased from Wako Pure Chemical Industries.
A radical-generating diamine represented by the following formula DA-8 was prepared as follows.
The diamine represented by the following formula DA-9 was prepared by the method described later in “(Raw Material Synthesis Example 3) Synthesis of DA-9”.
NMP:N-メチル-2-ピロリドン
BCS:ブチルセロソルブ
THF:テトラヒドロフラン
DMF:N,N-ジメチルホルムアミド
<添加剤>
3AMP:3-ピコリルアミン
以下、実施例を掲げて本発明を詳しく説明するが、本発明はこれらの実施例に限定されるものではない。
<重合性化合物>
下記式RM1~RM12及びRM13で表される重合性化合物。 <Solvent>
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve THF: Tetrahydrofuran DMF: N, N-dimethylformamide <Additive>
3 AMP:3-Picolylamine Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples.
<Polymerizable compound>
Polymerizable compounds represented by the following formulas RM1 to RM12 and RM13.
装置:センシュー科学社製 常温ゲル浸透クロマトグラフィー(GPC)装置(SSC-7200)、
カラム:Shodex社製カラム(KD-803、KD-805)、
カラム温度:50℃、
溶離液:N,N’-ジメチルホルムアミド(添加剤として、臭化リチウム-水和物(LiBr・H2O)が30mmol/L、リン酸・無水結晶(o-リン酸)が30mmol/L、テトラヒドロフラン(THF)が10ml/L)、
流速:1.0ml/分、
検量線作成用標準サンプル:東ソー社製 TSK 標準ポリエチレンオキサイド(分子量約9000,000、150,000、100,000、30,000)、および、ポリマーラボラトリー社製 ポリエチレングリコール(分子量 約12,000、4,000、1,000)。 Moreover, the molecular weight measurement conditions of polyimide are as follows.
Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd.
Column: Column manufactured by Shodex (KD-803, KD-805),
Column temperature: 50 ° C.
Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H 2 O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, Tetrahydrofuran (THF) at 10 ml / L),
Flow rate: 1.0 ml / min,
Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 9,000,150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight: about 12,000, 4) manufactured by Polymer Laboratory , 1,000, 1,000).
イミド化率(%)=(1-α・x/y)×100 Moreover, the imidation ratio of polyimide was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard φ5 by Kusano Kagaku Co., Ltd.), add 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05% TMS mixture), and apply ultrasonic waves. To dissolve completely. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum. The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value. In the following formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is the proton of the NH group of the amic acid in the case of polyamic acid (imidation rate is 0%). This is the ratio of the number of reference protons to one.
Imidization rate (%) = (1−α · x / y) × 100
下記合成例1~12に記載の生成物は1H-NMR分析により同定した(分析条件は下記の通り)。
装置:Varian NMR System 400 NB (400 MHz)
測定溶媒:CDCl3、DMSO-d6
基準物質:テトラメチルシラン(TMS)(δ0.0 ppm for 1H) <Synthesis of diamine and polymerizable compound>
The products described in Synthesis Examples 1 to 12 below were identified by 1 H-NMR analysis (analysis conditions are as follows).
Apparatus: Varian NMR System 400 NB (400 MHz)
Measurement solvent: CDCl 3, DMSO-d 6
Reference substance: Tetramethylsilane (TMS) (δ0.0 ppm for 1 H)
(原料合成例1-2)DA-6の合成 In a 500 mL four-necked flask, 21.2 g of 2-methylacrylic acid 6- [4- (2-hydroxycarbonylvinyl) phenyl] -hexyl ester, 300 mL of tetrahydrofuran, and 2- (2,4-dinitrophenyl) ethanol 13.6 g, 18.4 g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 0.8 g of 4-dimethylaminopyridine (DMAP) were added and stirred at room temperature. After completion of the reaction, the organic layer is extracted with ethyl acetate, anhydrous magnesium sulfate is added to the organic layer, dehydrated, dried, filtered, the solvent is distilled off using a rotary evaporator, and the residue is washed with isopropyl alcohol and dried. As a result, 15.9 g of the desired product DA-6-1 (yellowish white solid) was obtained (yield 47%).
(Raw Material Synthesis Example 1-2) Synthesis of DA-6
1H NMR (400 MHz,[D6]-DMSO):δ7.64-7.66 (d,2H), 7.58-7.62 (d,1H), 6.95-6.97 (d,2H), 6.60-6.62 (d,1H), 6.44-6.48 (d,1H), 6.02 (s,1H), 5.89 (s,1H), 5.78-5.81 (d,1H), 5.66 (s,1H), 4.65 (s,2H), 4.59 (s,2H), 4.08-4.17 (m,4H), 4.00-4.03 (t,2H), 2.65-2.69 (t,2H), 1.87 (s,3H), 1.62-1.74 (m,4H), 1.39-1.45 (m,4H)
(原料合成例2)DA-8の合成 To a 500 mL four-necked flask, 7.6 g of DA-6-1, 150 mL of ethyl acetate, 150 mL of pure water, 8.4 g of reduced iron, and 6.5 g of ammonium chloride were added and stirred while heating to 60 ° C. After completion of the reaction, reduced iron was filtered and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration and drying, and anhydrous magnesium sulfate was filtered. The solvent of the obtained filtrate was distilled off using a rotary evaporator. The residue was washed with isopropanol and dried to obtain 13.4 g of the desired product DA-6 (yellowish white solid) (yield 95%). The results of measuring the obtained solid by 1 H-NMR are shown below. From this result, it was confirmed that the obtained solid was the target DA-6.
1 H NMR (400 MHz, [D 6 ] -DMSO): δ7.64-7.66 (d, 2H), 7.58-7.62 (d, 1H), 6.95-6.97 (d, 2H), 6.60-6.62 (d, 1H), 6.44-6.48 (d, 1H), 6.02 (s, 1H), 5.89 (s, 1H), 5.78-5.81 (d, 1H), 5.66 (s, 1H), 4.65 (s, 2H), 4.59 (s, 2H), 4.08-4.17 (m, 4H), 4.00-4.03 (t, 2H), 2.65-2.69 (t, 2H), 1.87 (s, 3H), 1.62-1.74 (m, 4H), 1.39 -1.45 (m, 4H)
(Raw material synthesis example 2) Synthesis of DA-8
攪拌子と窒素導入管を備えた2L四口フラスコに、2,4-ジニトロフルオロベンゼンを100.0g([Mw:186.10g/mol]、0.538mol)、2-ヒドロキシ-4’-(2-ヒドロキシエトキシ)-2-メチルプロピオフェノンを120.6g([Mw:224.25g/mol]、0.538mol)、トリエチルアミンを81.7g([Mw:101.19g/mol]、0.807mol)、THFを1000g加え、24時間還流させた。反応終了後、ロータリーエバポレーターで濃縮し、酢酸エチルを加え、これを純水と生理食塩水にて数回洗浄した後、無水硫酸マグネシウムで乾燥させた。
無水硫酸マグネシウムを濾過にて取り除き、ロータリーエバポレーターにて濃縮した後、酢酸エチルとノルマルヘキサンにより再結晶し、乳白色の個体157.0g([Mw:390.34g/mol]、0.402mol、収率:75%)を得た。分子内水素原子の核磁気共鳴スペクトル(1H-NMRスペクトル)にて確認した。測定データを以下に示す。
1H NMR (400 MHz,CDCl3)δ:8.75(Ar:1H)、8.48~8.45(Ar:1H)、8.09~8.05(Ar:2H)、7.34~7.31(Ar:1H)7.00~6.96(Ar:2H)、4.65~4.63(-CH2-:2H)、4.52~4.49(-CH2-:2H)、4.16(-OH:1H)、1.66~1.60(-CH3×2、6H) Total:18H Step 1 Synthesis of 1- (4- (2,4-dinitrophenoxy) ethoxy) phenyl) -2-hydroxy-2-methylpropanone In a 2 L four-necked flask equipped with a stirrer and a nitrogen inlet tube, 2,4-dinitro 100.0 g of fluorobenzene ([Mw: 186.10 g / mol], 0.538 mol), 120.6 g of 2-hydroxy-4 ′-(2-hydroxyethoxy) -2-methylpropiophenone ([Mw: 224.25 g / mol], 0.538 mol), 81.7 g of triethylamine ([Mw: 101.19 g / mol], 0.807 mol) and 1000 g of THF were added and refluxed for 24 hours. After completion of the reaction, the mixture was concentrated on a rotary evaporator, ethyl acetate was added, and this was washed several times with pure water and physiological saline, and then dried over anhydrous magnesium sulfate.
After removing anhydrous magnesium sulfate by filtration and concentrating with a rotary evaporator, recrystallization with ethyl acetate and normal hexane gave 157.0 g of milky white solid ([Mw: 390.34 g / mol], 0.402 mol, yield) : 75%). It was confirmed by a nuclear magnetic resonance spectrum ( 1 H-NMR spectrum) of an intramolecular hydrogen atom. The measurement data is shown below.
1 H NMR (400 MHz, CDCl 3 ) δ: 8.75 (Ar: 1H), 8.48-8.45 (Ar: 1H), 8.09-8.05 (Ar: 2H), 7.34 To 7.31 (Ar: 1H) 7.00 to 6.96 (Ar: 2H), 4.65 to 4.63 (—CH 2 —: 2H), 4.52 to 4.49 (—CH 2 —) : 2H), 4.16 (—OH: 1H), 1.66 to 1.60 (—CH 3 × 2, 6H) Total: 18H
1L四口フラスコにStep1で得たジニトロベンゼン誘導体を100.0g([Mw:390.34g/mol]、0.256mol)と鉄がドープされた白金カーボン(Evonic社製 3wt%)を10.0g計り取り、THFを500ml加え、減圧脱気及び水素置換を十分に行い、室温で24時間反応させた。
反応終了後、PTFE製のメンブランフィルターにて白金カーボンを除去し、濾液をロータリーエバポレーターによって除去し、固体を析出させた。得られた固体をイソプロピルアルコールにて加熱洗浄を行い、更に減圧乾燥させることにより、目的の化合物である薄ピンク色の固体72.7g([Mw:330.38g/mol]、0.220mol収率:86%)を得た。1H-NMRスペクトル測定データを以下に示す。
1H NMR (400 MHz,CDCl3)δ:8.09~8.05(Ar:2H)、7.01~6.97(Ar:2H)、6.70~6.68(Ar:1H)、6.12(Ar:1H)、4.36~4.33(-CH2-:2H)、4.29~4.27(-OH&-CH2-:3H)、3.7(-NH2:2H)、3.39(-NH2:2H)、1.64~1.63(-CH3×2:6H) Total:22H.
(原料合成例3)DA-9の合成 Step 2 Synthesis of 1- (4- (2,4-diaminophenoxy) ethoxy) phenyl) -2-hydroxy-2-methylpropanone (DA-8) The dinitrobenzene derivative obtained in Step 1 was added to a 1 L four-necked flask in 100. Weigh 10.0 g ([Mw: 390.34 g / mol], 0.256 mol) and 10.0 g of iron-doped platinum carbon (3 wt% manufactured by Evonic), add 500 ml of THF, and perform vacuum degassing and hydrogen replacement. Fully conducted and allowed to react for 24 hours at room temperature.
After completion of the reaction, platinum carbon was removed with a PTFE membrane filter, and the filtrate was removed with a rotary evaporator to precipitate a solid. The obtained solid was heated and washed with isopropyl alcohol, and further dried under reduced pressure, whereby 72.7 g ([Mw: 330.38 g / mol], 0.220 mol yield) of the target compound was a light pink solid. : 86%). The 1 H-NMR spectrum measurement data is shown below.
1 H NMR (400 MHz, CDCl 3 ) δ: 8.09 to 8.05 (Ar: 2H), 7.01 to 6.97 (Ar: 2H), 6.70 to 6.68 (Ar: 1H) 6.12 (Ar: 1H), 4.36 to 4.33 (—CH 2 —: 2H), 4.29 to 4.27 (—OH & —CH 2 —: 3H), 3.7 (—NH 2 : 2H), 3.39 (—NH 2 : 2H), 1.64 to 1.63 (—CH 3 × 2: 6H) Total: 22H.
(Raw Material Synthesis Example 3) Synthesis of DA-9
1000mL四口フラスコに、THF600g中、コレステロール120g(310mmol,1.0eq)とトリエチルアミン33.3g(329mmol,1.1eq)を仕込み、3,5-ジニトロベンゾイルクロリド69.2g(300mmol)を1時間かけて添加した。添加後、終夜室温にて攪拌した後、水による再沈殿を行った。得られた固体をIPAと酢酸エチルでそれぞれ再結晶を行い、DA-9-1の粗物を179g得た(粗収率:100%)。
1H-NMR(CDCl3,δppm):9.22(s,1H),9.16(s,2H),5.46-5.44(m,1H),5.00-4.95(m,1H),2.56-2.48(m,2H),2.06-1.95(m,4H),1.87-1.81(m,2H),1.63-0.86(m,32H),0.70(s,3H). <Synthesis of DA-9-1>
A 1000 mL four-necked flask was charged with 120 g (310 mmol, 1.0 eq) of cholesterol and 33.3 g (329 mmol, 1.1 eq) of triethylamine in 600 g of THF, and 69.2 g (300 mmol) of 3,5-dinitrobenzoyl chloride was added over 1 hour. Added. After the addition, the mixture was stirred overnight at room temperature and then reprecipitated with water. The obtained solid was recrystallized with IPA and ethyl acetate, respectively, to obtain 179 g of a crude product of DA-9-1 (crude yield: 100%).
1 H-NMR (CDCl 3 , δ ppm): 9.22 (s, 1H), 9.16 (s, 2H), 5.46-5.44 (m, 1H), 5.00-4.95 ( m, 1H), 2.56-2.48 (m, 2H), 2.06-1.95 (m, 4H), 1.87-1.81 (m, 2H), 1.63-0. 86 (m, 32H), 0.70 (s, 3H).
2000mL四口フラスコに、THF750g及び純水750g中、DA-9-1を146g(251mmol)、塩化錫284g(1497mmol,6.0eq)を仕込み、70℃で終夜撹拌した。反応終了後、中和を行い、析出した錫をろ過により除去した。その後分液及びIPA にて再結晶を行い、DA-9を76.3g得た(収率:58%)。
1H-NMR(CDCl3,δppm):6.78(s,2H),6.18(s,1H),5.42-5.40(m,1H),4.84-4.77(m,1H),3.67(s,4H),2.43(d,2H),1.63-0.86(m,38H),0.69(s,3H).
<合成例1 -RM1の合成-> <Synthesis of DA-9>
In a 2000 mL four-necked flask, 146 g (251 mmol) of DA-9-1 and 284 g of tin chloride (1497 mmol, 6.0 eq) in 750 g of THF and 750 g of pure water were charged and stirred at 70 ° C. overnight. After completion of the reaction, neutralization was performed, and precipitated tin was removed by filtration. Thereafter, recrystallization was performed with liquid separation and IPA to obtain 76.3 g of DA-9 (yield: 58%).
1 H-NMR (CDCl 3 , δ ppm): 6.78 (s, 2H), 6.18 (s, 1H), 5.42-5.40 (m, 1H), 4.84-4.77 ( m, 1H), 3.67 (s, 4H), 2.43 (d, 2H), 1.63-0.86 (m, 38H), 0.69 (s, 3H).
<Synthesis Example 1 -Synthesis of RM1->
マグネチックスターラーを備えた1L四口フラスコに、THF350g及び水117g中、4-ブロモ-2-フルオロフェノール58.3g(305mmol)と4-(4,4,5,5-テトラメチル-1,3,2-ジオキサボロラン-2-イル)フェノール67.2g(1.0eq)、炭酸カリウム84.8g(2.0eq)、トリ(o-トリル)ホスフィン7.42g(8mol%)を仕込み、窒素置換後にビス(トリフェニルホスフィン)パラジウム(II)クロリド10.9g(5mol%)を加えて、65℃にて15時間反応させた。
反応終了後、減圧濃縮によりTHFを留去し、酢酸エチル466gで希釈後に3.0MHCl水溶液268gを加え、ろ過によりPd等の不溶物を除去し、さらに酢酸エチル233gを用いてフラスコやろ物の洗浄を行った。続いて、水相を分離して有機相回収し、回収した有機相を純水350gにより3度洗浄し、硫酸マグネシウムで脱水処理後、活性炭(銘柄:特製白鷺dry品 日本エンバイロケミカル製)2.92gを加えて室温で30分程撹拌し、ろ過乾燥することで粗物を得た。粗物をトルエン292gにより室温条件下で2度リパルプ洗浄後、ろ過乾燥することでRM1-A 42.0gを得た(収率:67%、性状:薄ピンク色の結晶)。
1H-NMR(400MHz) in DMSO-d6: 6.80 ppm(dd, J=2.0 Hz, J=6.8 Hz, 2H), 6.97 ppm (t, J=8.8 Hz, 1H), 7.21 ppm(dd, J=2.0 Hz, J=8.4 Hz, 1H), 7.35 ppm(dd, J=2,4 Hz, J=13.2 Hz, 1H), 7.42 ppm (dd, J=2.0 Hz, J=6.4 Hz, 2H), 9.49 ppm (s, 1H), 9.82 ppm (s, 1H). <Synthesis of RM1-A>
A 1 L four-necked flask equipped with a magnetic stirrer was charged with 58.3 g (305 mmol) of 4-bromo-2-fluorophenol and 4- (4,4,5,5-tetramethyl-1,3 in 350 g of THF and 117 g of water. , 2-Dioxaborolan-2-yl) phenol 67.2 g (1.0 eq), potassium carbonate 84.8 g (2.0 eq), tri (o-tolyl) phosphine 7.42 g (8 mol%), and after nitrogen substitution Bis (triphenylphosphine) palladium (II) chloride (10.9 g, 5 mol%) was added and reacted at 65 ° C. for 15 hours.
After completion of the reaction, THF was distilled off by concentration under reduced pressure. After dilution with 466 g of ethyl acetate, 268 g of 3.0 M HCl aqueous solution was added, and insoluble matters such as Pd were removed by filtration. Further, 233 g of ethyl acetate was used to wash the flask and filtrate. Went. Subsequently, the aqueous phase is separated and the organic phase is recovered, and the recovered organic phase is washed with 350 g of pure water three times, dehydrated with magnesium sulfate, and then activated carbon (brand: special white birch dry product manufactured by Nippon Enviro Chemical) 2. 92 g was added and stirred at room temperature for about 30 minutes, followed by filtration and drying to obtain a crude product. The crude product was washed with re-pulp twice at room temperature under 292 g of toluene, and then filtered and dried to obtain 42.0 g of RM1-A (yield: 67%, properties: light pink crystals).
1 H-NMR (400 MHz) in DMSO-d 6 : 6.80 ppm (dd, J = 2.0 Hz, J = 6.8 Hz, 2H), 6.97 ppm (t, J = 8.8 Hz, 1H), 7.21 ppm (dd, J = 2.0 Hz, J = 8.4 Hz, 1H), 7.35 ppm (dd, J = 2,4 Hz, J = 13.2 Hz, 1H), 7.42 ppm (dd, J = 2.0 Hz, J = 6.4 Hz, 2H), 9.49 ppm (s, 1H), 9.82 ppm (s, 1H).
マグネチックスターラーを備えた200ml四口フラスコに、アセトン80ml中、上記で得られた化合物(RM1-A)5.00g(24.5mmol)と2-(4-ブロモブチル)-1,3-ジオキソラン12.0g(2.2eq)、炭酸カリウム13.8g(4.0eq)を仕込み、60℃にて24時間反応させた。その後、反応溶液を純水に投入することで結晶を析出させ、ろ過乾燥することでRM1-B 10.4gを得た(収率:92%)。
1H-NMR(400MHz) in CDCl3:1.60-1.67 ppm(m, 4H), 1.71-1.78 ppm (m,4H), 1.82-1.93 ppm (m, 4H), 3.82-4.10 ppm(m, 12H), 4.89 ppm(t, J=4.6 Hz, 2H), 6.92-7.00 ppm(m, 3H), 7.20-7.30 ppm(m, 2H), 7.43 ppm(d, J=8.8Hz, 2H). <Synthesis of RM1-B>
In a 200 ml four-necked flask equipped with a magnetic stirrer, 5.00 g (24.5 mmol) of the compound (RM1-A) obtained above and 2- (4-bromobutyl) -1,3-dioxolane in 80 ml of acetone 0.0 g (2.2 eq) and potassium carbonate 13.8 g (4.0 eq) were charged and reacted at 60 ° C. for 24 hours. Thereafter, the reaction solution was poured into pure water to precipitate crystals, followed by filtration and drying to obtain 10.4 g of RM1-B (yield: 92%).
1 H-NMR (400 MHz) in CDCl 3 : 1.60-1.67 ppm (m, 4H), 1.71-1.78 ppm (m, 4H), 1.82-1.93 ppm (m, 4H), 3.82-4.10 ppm (m, 12H) , 4.89 ppm (t, J = 4.6 Hz, 2H), 6.92-7.00 ppm (m, 3H), 7.20-7.30 ppm (m, 2H), 7.43 ppm (d, J = 8.8Hz, 2H).
マグネチックスターラーを備えた100ml四口フラスコに、THF40ml中、上記で得られた化合物(RM1-B)2.90g(6.30mmol)と2-(ブロモメチル)アクリル酸2.5g(2.4eq)、塩化錫(無水物)2.8g(2.4eq)を仕込み、10%HCl水溶液12mlを加えて70℃にて20時間反応させた。その後、反応溶液を純水に投入することで結晶を析出させ、ろ過乾燥することで粗物を得た。得られた粗物をTHF/EtOH中で再結晶することでRM1 2.2gを得た(収率:69%)。
1H-NMR(400MHz) in CDCl3:1.55-1.93 ppm (m, 12H), 2.61 ppm (dd, J=7.6 Hz, J=18.4 Hz, 2H), 3.09 ppm(dd, J=6.8 Hz, J=16.6 Hz, 2H), 4.00 ppm (t, J=6.2 Hz, 2H), 4.08 ppm(t, J=6.4 Hz, 2H),4.35-4.60 ppm(m, 2H), 5.64 ppm (s, 2H), 6.24 ppm (s, 2H), 6.93-7.01 ppm (m, 3H), 7.22-7.289 ppm(m, 2H), 7.45 ppm(d, J=8.8Hz, 2H).
<合成例2 -RM2の合成-> <Synthesis of RM1>
In a 100 ml four-necked flask equipped with a magnetic stirrer, 2.90 g (6.30 mmol) of the compound (RM1-B) obtained above and 2.5 g (2.4 eq) of 2- (bromomethyl) acrylic acid in 40 ml of THF. Then, 2.8 g (2.4 eq) of tin chloride (anhydride) was added, and 12 ml of 10% HCl aqueous solution was added and reacted at 70 ° C. for 20 hours. Thereafter, the reaction solution was poured into pure water to precipitate crystals, and filtered and dried to obtain a crude product. The obtained crude product was recrystallized in THF / EtOH to obtain 2.2 g of RM1 (yield: 69%).
1 H-NMR (400 MHz) in CDCl 3 : 1.55-1.93 ppm (m, 12H), 2.61 ppm (dd, J = 7.6 Hz, J = 18.4 Hz, 2H), 3.09 ppm (dd, J = 6.8 Hz, J = 16.6 Hz, 2H), 4.00 ppm (t, J = 6.2 Hz, 2H), 4.08 ppm (t, J = 6.4 Hz, 2H), 4.35-4.60 ppm (m, 2H), 5.64 ppm (s, 2H) , 6.24 ppm (s, 2H), 6.93-7.01 ppm (m, 3H), 7.22-7.289 ppm (m, 2H), 7.45 ppm (d, J = 8.8Hz, 2H).
<Synthesis Example 2 -Synthesis of RM2->
マグネチックスターラーを備えた1L四口フラスコに、THF281g中、メタクリル酸2-ヒドロキシエチル70.2g(539mmol)、トリエチルアミン76.4g(1.4eq)を仕込み、氷冷攪拌下、THF35.1gで希釈したメタンスルホニルクロリド74.6g(1.2eq)を滴下した後、室温にて2時間撹拌した。その後、反応液から析出した塩をろ過し、ろ液にジブチルヒドロキシトルエン0.35gを添加し、濃縮乾燥した。次に、濃縮物残渣に酢酸エチル281gを加えて、純水210gを加えたところ、不溶物が発生したため、活性炭(銘柄:特製白鷺dry品 日本エンバイロケミカル製)3.5gを加え、室温にて30分間撹拌した。続いて、これをろ過し、不溶物が除去されたことを確認後、水相を除去した。さらに、有機相を純水210gで2回洗浄し、硫酸マグネシウムで脱水処理した後、濃縮乾燥し、RM2-A 99.0gを得た(収率:86%、性状:黄色液体)。
1H-NMR(400MHz) in CDCl3:1.93-1.94 ppm(m, 3H), 3.03 ppm(s, 3H), 4.39-4.41 ppm(m, 2H), 4.46-4.44 ppm(m, 2H), 5.61-5.62 ppm(m, 1H), 6.15(m, 1H). <Synthesis of RM2-A>
A 1 L four-necked flask equipped with a magnetic stirrer was charged with 70.2 g (539 mmol) of 2-hydroxyethyl methacrylate and 76.4 g (1.4 eq) of triethylamine in 281 g of THF, and diluted with 35.1 g of THF under stirring with ice cooling. After dropwise addition of 74.6 g (1.2 eq) of methanesulfonyl chloride, the mixture was stirred at room temperature for 2 hours. Thereafter, the salt precipitated from the reaction solution was filtered, and 0.35 g of dibutylhydroxytoluene was added to the filtrate, followed by concentration and drying. Next, when 281 g of ethyl acetate was added to the concentrate residue and 210 g of pure water was added, insoluble matter was generated, so 3.5 g of activated carbon (brand: special white birch dry product manufactured by Nihon Enviro Chemical) was added at room temperature. Stir for 30 minutes. Subsequently, this was filtered, and after confirming that insoluble matter was removed, the aqueous phase was removed. Further, the organic phase was washed twice with 210 g of pure water, dehydrated with magnesium sulfate, and concentrated and dried to obtain 99.0 g of RM2-A (yield: 86%, property: yellow liquid).
1 H-NMR (400 MHz) in CDCl 3 : 1.93-1.94 ppm (m, 3H), 3.03 ppm (s, 3H), 4.39-4.41 ppm (m, 2H), 4.46-4.44 ppm (m, 2H), 5.61 -5.62 ppm (m, 1H), 6.15 (m, 1H).
マグネチックスターラーを備えた300ml四口フラスコに、THF72.8g及び純水31.2g中、4-ブロモ-2-フルオロフェノール10.4g(54.4mmol)と6-ヒドロキシ-2-ナフタレンボロン酸9.68g(1.0eq)、炭酸カリウム15.1g(2.0eq)、トリ(o-トリル)ホスフィン1.32g(8mol%)を仕込み、窒素置換後にビス(トリフェニルホスフィン)パラジウム(II)クロリド1.91g(5mol%)を加えて、65℃で2時間反応させた。その後、減圧濃縮によりTHF除去し、酢酸エチル104gで希釈後3.0 M HCl水溶液47.8gを加えて撹拌した。続いて、ろ過によりPdを除去し、さらに酢酸エチル52.0gをろ物等を洗浄後、水相を分離した。回収した有機相を純水72.8gによりで3度洗浄し、硫酸マグネシウムで脱水処理した後、活性炭(銘柄:特製白鷺dry品 日本エンバイロケミカル製)0.52gを加えて室温で1時間程撹拌し、ろ過乾燥した。粗物をトルエン72.8gでリパルプ洗浄後、シリカゲルカラムクロマトグラフィー(酢酸エチル/トルエン/ヘキサン(=1 /1 /2vol))により精製することでRM2-B 6.47gを得た(収率:49%、性状:白色固体)。
1H-NMR(400MHz) in DMSO-d6:7.03-7.13 ppm(m, 3H), 7.42-7.40 ppm(m, 1H), 7.57 ppm(dd, J=13 Hz, J=2.2 Hz, 1H), 7.67 ppm(dd, J=8.6 Hz, J=1.8 Hz, 1H), 7.72 ppm(d, J=8.4 Hz, 1H), 7.80 ppm(d, J=8.4 Hz, 1H), 8.01 ppm(s, 1H), 9.78 ppm(s, 1H), 9.96 ppm(s, 1H) <Synthesis of RM2-B>
In a 300 ml four-necked flask equipped with a magnetic stirrer, 10.4 g (54.4 mmol) of 4-bromo-2-fluorophenol and 6-hydroxy-2-naphthaleneboronic acid 9 in 72.8 g of THF and 31.2 g of pure water .68 g (1.0 eq), potassium carbonate 15.1 g (2.0 eq), tri (o-tolyl) phosphine 1.32 g (8 mol%) were charged, and after nitrogen substitution, bis (triphenylphosphine) palladium (II) chloride 1.91 g (5 mol%) was added and reacted at 65 ° C. for 2 hours. Thereafter, THF was removed by concentration under reduced pressure, diluted with 104 g of ethyl acetate, and 47.8 g of 3.0 M HCl aqueous solution was added and stirred. Subsequently, Pd was removed by filtration, and 52.0 g of ethyl acetate was washed with the filtrate and the aqueous phase was separated. The recovered organic phase was washed 3 times with 72.8 g of pure water, dehydrated with magnesium sulfate, 0.52 g of activated carbon (brand: special white birch dry product, Nippon Enviro Chemical) was added, and the mixture was stirred at room temperature for about 1 hour. Filtered and dried. The crude product was repulped with 72.8 g of toluene and purified by silica gel column chromatography (ethyl acetate / toluene / hexane (= 1 1/2 vol)) to obtain 6.47 g of RM2-B (yield: 49 %, Property: white solid).
1 H-NMR (400 MHz) in DMSO-d 6 : 7.03-7.13 ppm (m, 3H), 7.42-7.40 ppm (m, 1H), 7.57 ppm (dd, J = 13 Hz, J = 2.2 Hz, 1H) , 7.67 ppm (dd, J = 8.6 Hz, J = 1.8 Hz, 1H), 7.72 ppm (d, J = 8.4 Hz, 1H), 7.80 ppm (d, J = 8.4 Hz, 1H), 8.01 ppm (s, 1H), 9.78 ppm (s, 1H), 9.96 ppm (s, 1H)
マグネチックスターラーを備えた200mL四口フラスコに、DMF48.6g中、上記で得られた化合物(RM2-B)6.07g(23.9mmol)と重合性側鎖(RM2-A)11.1g(2.2eq)、炭酸カリウム9.93g(3.0eq)を仕込み、窒素雰囲気下65℃で22時間反応させた。
その後、酢酸エチル48.6gで反応溶液を希釈後、ろ過により無機塩を除去後、ろ物を酢酸エチル42.5gで洗浄した。回収した有機相を純水48.6gで3回洗浄し、有機相を硫酸マグネシウムで脱水処理した後、濃縮乾燥した。乾燥後、回収した粗物に2,6-ジ-tert-ブチル-p-クレゾール12.1mgを添加し、THF5.77gを加えて45℃で加熱することで完全に溶解させ、メタノール35.8gを加えて5.0℃で再結晶を行った。しかし、不純物が確認されたため回収した固体にTHF4.89gを加えて45℃で加熱することで完全に溶解させ、メタノール24.9gを加えて室温で再結晶することでRM2 6.37gを得た(収率:56%、性状:白色結晶)。
1H-NMR(400MHz) in DMSO-d6:1.89 ppm(s, 6H), 4.38-4.42 ppm(m, 4H), 4.46-2.47 ppm(m, 2H), 4.49-4.51 ppm(m, 2H),5.70-5.71 ppm(m, 2H), 6.05 ppm(d, J=6.8 Hz, 2H),7.22 ppm(dd, J=9.0 Hz, J=2.8 Hz, 1H), 7.33 ppm(t, J=9.0 Hz, 1H), 7.40 ppm(d, J=2.4 Hz, 1H), 7.59 ppm(d, J=9.6Hz, 1H), 7.70 ppm (dd, J=12.8 Hz, J=2.0 Hz, 1H), 7.80 ppm (dd, J=8.6 Hz, J=1.8 Hz, 1H), 7.88 ppm (t, J=9.2 Hz, 2H), 8.15 ppm (s, 1H). <Synthesis of RM2>
In a 200 mL four-necked flask equipped with a magnetic stirrer, 6.07 g (23.9 mmol) of the compound (RM2-B) obtained above and 11.1 g of a polymerizable side chain (RM2-A) in 48.6 g of DMF ( 2.2 eq) and 9.93 g (3.0 eq) of potassium carbonate were charged and reacted at 65 ° C. for 22 hours under a nitrogen atmosphere.
Thereafter, the reaction solution was diluted with 48.6 g of ethyl acetate, inorganic salts were removed by filtration, and the residue was washed with 42.5 g of ethyl acetate. The recovered organic phase was washed 3 times with 48.6 g of pure water, and the organic phase was dehydrated with magnesium sulfate and concentrated and dried. After drying, 12.1 mg of 2,6-di-tert-butyl-p-cresol is added to the recovered crude product, and 5.77 g of THF is added and heated at 45 ° C. to completely dissolve, 35.8 g of methanol. And was recrystallized at 5.0 ° C. However, since impurities were confirmed, 4.89 g of THF was added to the collected solid and completely dissolved by heating at 45 ° C., and 24.9 g of methanol was added and recrystallized at room temperature to obtain 6.37 g of RM2. (Yield: 56%, property: white crystals).
1 H-NMR (400 MHz) in DMSO-d 6 : 1.89 ppm (s, 6H), 4.38-4.42 ppm (m, 4H), 4.46-2.47 ppm (m, 2H), 4.49-4.51 ppm (m, 2H) , 5.70-5.71 ppm (m, 2H), 6.05 ppm (d, J = 6.8 Hz, 2H), 7.22 ppm (dd, J = 9.0 Hz, J = 2.8 Hz, 1H), 7.33 ppm (t, J = 9.0 Hz, 1H), 7.40 ppm (d, J = 2.4 Hz, 1H), 7.59 ppm (d, J = 9.6 Hz, 1H), 7.70 ppm (dd, J = 12.8 Hz, J = 2.0 Hz, 1H), 7.80 ppm (dd, J = 8.6 Hz, J = 1.8 Hz, 1H), 7.88 ppm (t, J = 9.2 Hz, 2H), 8.15 ppm (s, 1H).
メカニカルスターラーを備えた2L四口フラスコに、THF179g及び純水76.6g中、1,4-ジブロモ-2-フルオロベンゼン25.5g(101mmol)、4-(4,4,5,5-テトラメチル-1,3,2-ジオキサボロラン-2-イル)フェノール45.5g(2.0eq)、炭酸カリウム41.7g(3.0eq)、ビス(トリフェニルホスフィン)パラジウム(II)クロリド2.12gを仕込み、窒素雰囲気下65℃にて24時間撹拌した。その後、減圧濃縮にすることでTHFを留去し、反応溶液を酢酸エチル255gで希釈し、3.0M HCl水溶液99.5gを加え、ろ過によりPd等の不溶物を除去した。ろ液から水相を除去後、得られた有機相を純水179gで3回洗浄した。回収した有機相を硫酸マグネシウムで脱水処理し、活性炭(銘柄:特製白鷺dry品 日本エンバイロケミカル製)1.30gを加えて室温条件下で30分程攪拌した後、ろ過乾燥することで粗物を得た。回収した粗物をトルエン153gに懸濁させ、60℃で1時間リパルプ洗浄を2度行い、ろ過乾燥することでRM3-A 22.4gを得た(収率:79%、性状:薄ピンク色結晶)。
1H-NMR(400MHz) in DMSO-d6:6.85-6.88 ppm(m, 4H), 7.41 ppm(dd, J=1.2 Hz J=8.4 Hz , 2H), 7.46-7.49 ppm(m, 3H), 7.57 ppm(d, J=8.8 Hz, 2H), 9.65 ppm(s, 2H). <Synthesis of RM3-A>
In a 2 L four-necked flask equipped with a mechanical stirrer, 25.5 g (101 mmol) of 1,4-dibromo-2-fluorobenzene, 4- (4,4,5,5-tetramethyl) in 179 g of THF and 76.6 g of pure water. -1,3,2-Dioxaborolan-2-yl) phenol 45.5 g (2.0 eq), potassium carbonate 41.7 g (3.0 eq), bis (triphenylphosphine) palladium (II) chloride 2.12 g The mixture was stirred at 65 ° C. for 24 hours under a nitrogen atmosphere. Then, THF was distilled off by concentration under reduced pressure, the reaction solution was diluted with 255 g of ethyl acetate, 3.0M HCl aqueous solution 99.5 g was added, and insoluble matters such as Pd were removed by filtration. After removing the aqueous phase from the filtrate, the obtained organic phase was washed 3 times with 179 g of pure water. The recovered organic phase is dehydrated with magnesium sulfate, 1.30 g of activated carbon (brand name: special white lees dry product, Nippon Enviro Chemical) is added, and the mixture is stirred for about 30 minutes at room temperature. Obtained. The recovered crude product was suspended in 153 g of toluene, repulp washed at 60 ° C. for 1 hour twice, filtered and dried to obtain 22.4 g of RM3-A (yield: 79%, property: light pink) crystal).
1 H-NMR (400 MHz) in DMSO-d6: 6.85-6.88 ppm (m, 4H), 7.41 ppm (dd, J = 1.2 Hz J = 8.4 Hz, 2H), 7.46-7.49 ppm (m, 3H), 7.57 ppm (d, J = 8.8 Hz, 2H), 9.65 ppm (s, 2H).
メカニカルスターラーを備えた500mL四口フラスコに、DMF113g中、重合性側鎖(RM2-A)23.0g(2.2eq)と上記で得られた化合物(RM3-A)14.1g(50.2mmol)、炭酸カリウム20.9g(3.0eq)を仕込み、窒素雰囲気下65℃にて18時間撹拌した。18時間後、原料が残存していたため重合性側鎖(RM2-A)(0.2eq/2)を追加して更に4時間反応させた。その後、反応溶液を酢酸エチル113gで希釈後、ろ過により無機塩を除去後、ろ物を酢酸エチル70.5gで洗浄した。回収した有機相を純水141gで洗浄した結果、微量の白色結晶が生じたため、酢酸エチル70.5gを追加して、更に純水141gで2回洗浄し、有機相を硫酸マグネシウムで脱水処理し、ろ過乾燥した。回収した粗物に活性炭(銘柄:特製白鷺dry品 日本エンバイロケミカル製)0.71gを加えて室温条件下で30分程撹拌した後、ろ過乾燥し、酢酸エチル222gを加えて50℃で加熱することで完全に溶解させ、ヘキサン98.2gを加え、2℃で再結晶することでRM3 15.0gを得た(収率:59%、性状:白色結晶)。
1H-NMR(400MHz) in DMSO-d6:1.89 ppm(s, 6H), 4.30-4.33 ppm(m, 4H), 4.45-4.46 ppm(m, 4H), 5.71 ppm(s, 2H), 6.05 ppm(s, 2H), 7.07-7.10 ppm(m, 4H), 7.52-7.56 ppm(m, 5H), 7.70 ppm(d, J=8.4 Hz, 2H). <Synthesis of RM3>
In a 500 mL four-necked flask equipped with a mechanical stirrer, 23.0 g (2.2 eq) of a polymerizable side chain (RM2-A) and 14.1 g (50.2 mmol) of the compound (RM3-A) obtained above in DMF 113 g ), 20.9 g (3.0 eq) of potassium carbonate, and stirred at 65 ° C. for 18 hours under a nitrogen atmosphere. After 18 hours, since the raw material remained, a polymerizable side chain (RM2-A) (0.2 eq / 2) was added, and the reaction was further continued for 4 hours. Thereafter, the reaction solution was diluted with 113 g of ethyl acetate, inorganic salts were removed by filtration, and the residue was washed with 70.5 g of ethyl acetate. As a result of washing the recovered organic phase with 141 g of pure water, a small amount of white crystals was formed. Therefore, 70.5 g of ethyl acetate was added, and further washed with 141 g of pure water twice, and the organic phase was dehydrated with magnesium sulfate. , Filtered and dried. Add 0.71 g of activated carbon (brand: special white dried product manufactured by Nippon Enviro Chemical) to the recovered crude product, stir for about 30 minutes at room temperature, filter dry, add 222 g of ethyl acetate and heat at 50 ° C. This was completely dissolved, 98.2 g of hexane was added, and 15.0 g of RM3 was obtained by recrystallization at 2 ° C. (yield: 59%, property: white crystals).
1 H-NMR (400 MHz) in DMSO-d6: 1.89 ppm (s, 6H), 4.30-4.33 ppm (m, 4H), 4.45-4.46 ppm (m, 4H), 5.71 ppm (s, 2H), 6.05 ppm (s, 2H), 7.07-7.10 ppm (m, 4H), 7.52-7.56 ppm (m, 5H), 7.70 ppm (d, J = 8.4 Hz, 2H).
マグネチックスターラーを備えた300mL四口フラスコに、DMF73.4g中、F含有ビフェノール化合物(RM1-A)9.18g(45.0mmol)と炭酸カリウム18.6g(3.0eq)、重合性側鎖(RM2-A)20.7g(2.2eq)を仕込み、窒素雰囲気下62℃で15時間反応させた。その後、反応溶液を酢酸エチル138gで希釈し、ろ過により無機塩を除去した。回収したろ液に更に酢酸エチル45.9gを加えて、純水91.8gで3回洗浄し、硫酸ナトリウムで脱水処理した。続いて、活性炭(銘柄:特製白鷺dry品 日本エンバイロケミカル製)0.46gを加えて室温にて30分程撹拌した後、これをろ過し、ろ液を濃縮乾燥した。濃縮物に2,6-ジ-tert-ブチル-p-クレゾール9.2mgを添加し、IPA184gを加えて57℃まで加熱することで完全溶解させ、室温条件下で再結晶を行い、RM4 13.4gを得た(収率:70%、性状:薄黄色結晶)。
1H-NMR(400MHz) in DMSO-d6:1.87-1.88 ppm(m, 6H), 4.27-4.29 ppm(m, 2H), 4.34-4.37 ppm(m,2H), 4.43-4.46 ppm(m, 4H), 5.69-5.70 ppm(m, 2H), 6.03 ppm(d, J=4.8 Hz, 2H), 7.03 ppm(d, J=8.8 Hz, 2H), 7.25 ppm (t, J=8.8 Hz, 1H), 7.39 ppm(dd, J=1.6 Hz, J=8.4 Hz, 1H), 7.50 ppm(dd, J=2.0Hz, J=13 Hz, 1H), 7.58 ppm(d, J=8.8 Hz, 2H). <Synthesis of RM4>
In a 300 mL four-necked flask equipped with a magnetic stirrer, 9.18 g (45.0 mmol) of F-containing biphenol compound (RM1-A) and 18.6 g (3.0 eq) of potassium carbonate in 73.4 g of DMF, polymerizable side chain 20.7 g (2.2 eq) of (RM2-A) was charged and reacted at 62 ° C. for 15 hours under a nitrogen atmosphere. Thereafter, the reaction solution was diluted with 138 g of ethyl acetate, and inorganic salts were removed by filtration. Further, 45.9 g of ethyl acetate was added to the collected filtrate, washed with 91.8 g of pure water three times, and dehydrated with sodium sulfate. Subsequently, 0.46 g of activated carbon (brand name: special white birch dry product manufactured by Nippon Enviro Chemical) was added and stirred at room temperature for about 30 minutes, followed by filtration, and the filtrate was concentrated and dried. 9.2 mg of 2,6-di-tert-butyl-p-cresol was added to the concentrate, 184 g of IPA was added, and the mixture was completely dissolved by heating to 57 ° C., recrystallized at room temperature, and RM4 13. 4 g was obtained (yield: 70%, property: pale yellow crystals).
1 H-NMR (400 MHz) in DMSO-d6: 1.87-1.88 ppm (m, 6H), 4.27-4.29 ppm (m, 2H), 4.34-4.37 ppm (m, 2H), 4.43-4.46 ppm (m, 4H ), 5.69-5.70 ppm (m, 2H), 6.03 ppm (d, J = 4.8 Hz, 2H), 7.03 ppm (d, J = 8.8 Hz, 2H), 7.25 ppm (t, J = 8.8 Hz, 1H) , 7.39 ppm (dd, J = 1.6 Hz, J = 8.4 Hz, 1H), 7.50 ppm (dd, J = 2.0 Hz, J = 13 Hz, 1H), 7.58 ppm (d, J = 8.8 Hz, 2H).
WO2012/002513号の段落[0179]の記載に従って合成した。
<合成例6 -RM6の合成->
WO2012/133820号の段落[0163]の記載に従って合成した。 <Synthesis Example 5 -Synthesis of RM5->
It was synthesized according to the description in paragraph [0179] of WO2012 / 002513.
<Synthesis Example 6 -Synthesis of RM6->
It was synthesized according to the description in paragraph [0163] of WO2012 / 133820.
マグネチックスターラーを備えた200mL四口フラスコに、NMP18g中、F含有ビフェノール化合物(RM1-A)9.00g(44.1mmol)、ブロモアセトアルデヒドジメチルアセタール22.4g(3.0eq)、炭酸カリウム24.4g(4.0eq)、ヨウ化カリウム2.2g(0.30eq)を仕込み、120℃にて18時間攪拌した。18時間後にブロモアセトアルデヒドジメチルアセタール7.45g(1.0eq)、ヨウ化カリウム1.4g(0.2eq)を追加し更に8時間攪拌した。反応終了後、反応溶液をTHF99.0gで希釈し、無機塩をろ過した後、ろ液を減圧濃縮した。次に、この残渣を酢酸エチル198gで希釈し、純水99.0gで2回洗浄後、硫酸マグネシウムで脱水処理した。その後、活性炭(銘柄:特製白鷺dry品 日本エンバイロケミカル製)0.45gを加えて室温にて1時間撹拌し、これをろ過し、ろ液を減圧濃縮した。続いて、得られた粗物にTHF19.8gを加え50℃にて溶解させた後、IPA60.3gを加え、氷冷下攪拌した。これにより析出した結晶を、ろ過乾燥し、RM7-A 11.5gを得た(収率:62%、性状:薄茶色結晶)
1H-NMR(400MHz) in DMSO-d6: 3.36 ppm(m, 12H), 4.01 ppm (d, J=5.2 Hz, 2H), 4.08 ppm(d, J=5.2 Hz, 2H), 4.74-4.69 ppm(m, 2H), 7.03 ppm (d, J=11.6 Hz 2H), 7.25 ppm (t, J=8.8 Hz 1H),7.40-7.37 ppm(m, 1H) , 7.51 ppm (dd, J=13Hz, J=2.2 Hz 1H), 7.58 ppm (d, J=8.4 Hz 2H) <Synthesis of RM7-A->
In a 200 mL four-necked flask equipped with a magnetic stirrer, 9.00 g (44.1 mmol) of F-containing biphenol compound (RM1-A), 22.4 g (3.0 eq) of bromoacetaldehyde dimethyl acetal, and potassium carbonate 24. 4 g (4.0 eq) and potassium iodide 2.2 g (0.30 eq) were charged and stirred at 120 ° C. for 18 hours. After 18 hours, 7.45 g (1.0 eq) of bromoacetaldehyde dimethyl acetal and 1.4 g (0.2 eq) of potassium iodide were added, and the mixture was further stirred for 8 hours. After completion of the reaction, the reaction solution was diluted with 99.0 g of THF, the inorganic salt was filtered, and the filtrate was concentrated under reduced pressure. Next, this residue was diluted with 198 g of ethyl acetate, washed twice with 99.0 g of pure water, and dehydrated with magnesium sulfate. Thereafter, 0.45 g of activated carbon (brand: special white birch dry product manufactured by Nippon Enviro Chemical) was added and stirred at room temperature for 1 hour, this was filtered, and the filtrate was concentrated under reduced pressure. Subsequently, 19.8 g of THF was added to the obtained crude product and dissolved at 50 ° C., then 60.3 g of IPA was added, and the mixture was stirred under ice cooling. The crystals thus precipitated were filtered and dried to obtain 11.5 g of RM7-A (yield: 62%, property: light brown crystals).
1 H-NMR (400 MHz) in DMSO-d 6 : 3.36 ppm (m, 12H), 4.01 ppm (d, J = 5.2 Hz, 2H), 4.08 ppm (d, J = 5.2 Hz, 2H), 4.74-4.69 ppm (m, 2H), 7.03 ppm (d, J = 11.6 Hz 2H), 7.25 ppm (t, J = 8.8 Hz 1H), 7.40-7.37 ppm (m, 1H), 7.51 ppm (dd, J = 13Hz, J = 2.2 Hz 1H), 7.58 ppm (d, J = 8.4 Hz 2H)
マグネチックスターラーを備えた500mL四口フラスコに、THF103g中、上記で得られた化合物(RM7-A)10.4g(27.2mmol)、2-(ブロモメチル)アクリル酸エチル11.6g(2.2eq)、塩化錫12.4g(2.4eq)、10wt%HCl水溶液36.2gを仕込み、70℃にて39時間攪拌した。反応終了後、2,6-ジ-tert-ブチル-p-クレゾール30mgを添加し、THFを減圧留去し、酢酸エチル104gで希釈した。これにより分離した水相を除去後、40℃にて有機相を純水62.4gで3回洗浄した。次に、有機相を硫酸マグネシウムで脱水処理した後、活性炭(銘柄:特製白鷺dry品 日本エンバイロケミカル製)0.52gを加え室温にて1時間撹拌し、これをろ過し、ろ液を減圧濃縮去した。続いて得られた粗物にTHF52gを加え60℃にて溶解させた後、EtOH156gを加え、氷冷下攪拌した。これにより、析出した結晶をろ過乾燥し、RM7 3.42gを得た(収率:30%、性状:白色結晶)。
1H-NMR(400MHz) in DMSO-d6: 2.88-2.50 ppm(m, 2H), 3.17-2.11 ppm(m, 2H), 4.14 ppm (dd, J=5.6 Hz, 11.2 Hz, 1H), 4.28-4.20ppm(m, 2H), 4.33ppm(dd, J=2.8 Hz, 11.0 Hz, 1H), 5.00-4.95ppm(m, 2H), 6.99ppm(d, J=6.8 Hz, 2H), 7.22ppm(t, J=8.8Hz, 1H), 7.41ppm(d, J=8.4Hz, 1H), 7.52 ppm(dd, J=2Hz, 12.8Hz, 1H), 7.61ppm(d, J=2.0Hz, 2H) <Synthesis of RM7>
In a 500 mL four-necked flask equipped with a magnetic stirrer, 10.4 g (27.2 mmol) of the compound (RM7-A) obtained above in 103 g of THF and 11.6 g (2.2 eq) of ethyl 2- (bromomethyl) acrylate were obtained. ), 12.4 g (2.4 eq) of tin chloride, 36.2 g of 10 wt% HCl aqueous solution, and stirred at 70 ° C. for 39 hours. After completion of the reaction, 30 mg of 2,6-di-tert-butyl-p-cresol was added, THF was distilled off under reduced pressure, and diluted with 104 g of ethyl acetate. After removing the aqueous phase thus separated, the organic phase was washed 3 times with 62.4 g of pure water at 40 ° C. Next, after dehydrating the organic phase with magnesium sulfate, 0.52 g of activated carbon (brand: special white birch dry product manufactured by Nippon Enviro Chemical) was added and stirred at room temperature for 1 hour, this was filtered, and the filtrate was concentrated under reduced pressure. Left. Subsequently, 52 g of THF was added to the obtained crude product and dissolved at 60 ° C., 156 g of EtOH was added, and the mixture was stirred under ice cooling. Thereby, the precipitated crystals were filtered and dried to obtain 3.42 g of RM7 (yield: 30%, property: white crystals).
1 H-NMR (400 MHz) in DMSO-d 6 : 2.88-2.50 ppm (m, 2H), 3.17-2.11 ppm (m, 2H), 4.14 ppm (dd, J = 5.6 Hz, 11.2 Hz, 1H), 4.28 -4.20ppm (m, 2H), 4.33ppm (dd, J = 2.8 Hz, 11.0 Hz, 1H), 5.00-4.95ppm (m, 2H), 6.99ppm (d, J = 6.8 Hz, 2H), 7.22ppm (t, J = 8.8Hz, 1H), 7.41ppm (d, J = 8.4Hz, 1H), 7.52ppm (dd, J = 2Hz, 12.8Hz, 1H), 7.61ppm (d, J = 2.0Hz, 2H )
マグネチックスターラーを備えた200mL四口フラスコに、NMP15.3g中、F含有ビフェノール化合物(RM1-A)10.0g(53.7mmol)、炭酸カリウム20.4g(3.0eq)、ヨウ化カリウム1.61g(0.20eq)を仕込み、窒素雰囲気下80℃にてNMP5.30gで希釈した4-クロロブチルアルデヒドジメチルアセタール16.6g(2.2eq)を3時間かけて滴下した。滴下19時間後、4-クロロブチルアルデヒドジメチルアセタール2.25g(0.3eq)とヨウ化カリウム1.61g(0.2eq)を追加し、更に25時間反応させた。反応終了後、酢酸エチル80.0gで反応溶液を希釈し、ろ過により炭酸カリウムを除去した。更に酢酸エチル20.0gを追加して、純水60.0gで3回洗浄後、硫酸マグネシウムで脱水処理した。その後、減圧濃縮により溶媒を除去することで粗物を得た。得られた粗物をTHF10g及びMeOH70gを加えて50℃で加熱し、氷冷することで結晶を析出させ、ろ過乾燥することでRM8-A 11.7gを得た(収率:55%、性状:白色固体)。また、ろ液を減圧濃縮し溶媒を除去し、粗物をTHF5g及びIPA70gを加えて40℃で加熱し、氷冷することで結晶を析出させ、RM8-A 3.0gを得た(収率14%、性状:薄黄色固体)。
1H-NMR(400MHz) in DMSO-d6 : 1.77-1.67 ppm(m, 8H), 3.23 ppm(s, 12H), 4.01 ppm(t, J=6 Hz, 2H), 4.08 ppm(t, J=6 Hz, 2H), 4.44-4.41 ppm(m, 2H), 6.97 ppm(d, J=6.8 Hz, 2H), 7.19 ppm(t, J=8.8 Hz, 1H), 7.38 ppm(d, J=7.6 Hz, 1H), 7.48 ppm(dd, J=13.2 Hz, 2.4 Hz, 1H), 7.56 ppm(d, J=8.8 Hz, 2H) <Synthesis of RM8-A>
In a 200 mL four-necked flask equipped with a magnetic stirrer, 10.0 g (53.7 mmol) of an F-containing biphenol compound (RM1-A) in 15.3 g of NMP, 20.4 g (3.0 eq) of potassium carbonate, 1 potassium iodide .61 g (0.20 eq) was charged, and 16.6 g (2.2 eq) of 4-chlorobutyraldehyde dimethyl acetal diluted with 5.30 g of NMP was added dropwise at 80 ° C. in a nitrogen atmosphere over 3 hours. 19 hours after the dropwise addition, 2.25 g (0.3 eq) of 4-chlorobutyraldehyde dimethyl acetal and 1.61 g (0.2 eq) of potassium iodide were added, and the mixture was further reacted for 25 hours. After completion of the reaction, the reaction solution was diluted with 80.0 g of ethyl acetate, and potassium carbonate was removed by filtration. Further, 20.0 g of ethyl acetate was added, washed 3 times with 60.0 g of pure water, and dehydrated with magnesium sulfate. Thereafter, the solvent was removed by concentration under reduced pressure to obtain a crude product. To the obtained crude product, 10 g of THF and 70 g of MeOH were added and heated at 50 ° C., and the crystals were precipitated by cooling with ice, and 11.7 g of RM8-A was obtained by filtration and drying (yield: 55%, properties). : White solid). The filtrate was concentrated under reduced pressure to remove the solvent, and the crude product was added with 5 g of THF and 70 g of IPA, heated at 40 ° C., and cooled with ice to precipitate crystals to obtain 3.0 g of RM8-A (yield) 14%, property: pale yellow solid).
1 H-NMR (400 MHz) in DMSO-d 6 : 1.77-1.67 ppm (m, 8H), 3.23 ppm (s, 12H), 4.01 ppm (t, J = 6 Hz, 2H), 4.08 ppm (t, J = 6 Hz, 2H), 4.44-4.41 ppm (m, 2H), 6.97 ppm (d, J = 6.8 Hz, 2H), 7.19 ppm (t, J = 8.8 Hz, 1H), 7.38 ppm (d, J = 7.6 Hz, 1H), 7.48 ppm (dd, J = 13.2 Hz, 2.4 Hz, 1H), 7.56 ppm (d, J = 8.8 Hz, 2H)
マグネチックスターラーを備えた300mL四口フラスコに、THF133g中、上記で得られた化合物(RM8-A)13.2g(30.3mmol)、2-(ブロモメチル)アクリル酸エチル12.9g(2.2eq)、塩化錫13.8g(2.4eq)、10wt%HCl水溶液46.3gを仕込み、50℃で5時間反応させた。5時間後、20wt%HCl水溶液13.2gを加え、19時間反応させた。反応終了後、THFを減圧留去し、酢酸エチル106gで希釈後に純水52.8gで3回水洗浄した。続いて、更に酢酸エチル26.4gと純水79.2gを加え、炭酸水素ナトリウムを加えて中和した。中和後、塩をろ過により除去し、ろ液に活性炭(銘柄:特製白鷺dry品 日本エンバイロケミカル製)0.70gを加えて室温で撹拌し、ろ過した。得られた溶液を純水66gで2度洗浄後、減圧濃縮により溶媒を除去し、THF79.2g及びIPA158gを加えて50℃で加熱し、氷冷することで結晶を析出させ、ろ過することで結晶を回収した。得られた結晶を、THF46.2g及びMeOH92.4gを加えて50℃で加熱し、氷冷することで結晶を析出させ、ろ過乾燥することでRM8 8.92gを得た(収率:61%、性状:白色結晶)。
1H-NMR(400MHz) in CDCl3: 2.02-1.87 ppm(m, 8H), 2.67-2.60 ppm(m, 2H), 3.15-3.08 ppm(m, 2H), 4.13-4.02 ppm(m, 4H), 4.65-4.60 ppm(m, 2H), 5.66 ppm(s, 2H), 6.25 ppm(d, J=2.4 Hz, 2H), 6.94 ppm(d, J=8.8 Hz, 2H), 6.99 ppm(t, J=8.6 Hz, 1H) 7.28-7.22 ppm(m, 2H), 7.44 ppm(d, J=8.8 Hz, 2H) <Synthesis of RM8>
In a 300 mL four-necked flask equipped with a magnetic stirrer, 13.2 g (30.3 mmol) of the compound (RM8-A) obtained above in 133 g of THF, 12.9 g of ethyl 2- (bromomethyl) acrylate (2.2 eq) ), 13.8 g (2.4 eq) of tin chloride, and 46.3 g of 10 wt% aqueous HCl solution were charged and reacted at 50 ° C. for 5 hours. After 5 hours, 13.2 g of a 20 wt% aqueous HCl solution was added and allowed to react for 19 hours. After completion of the reaction, THF was distilled off under reduced pressure, diluted with 106 g of ethyl acetate, and washed with water 52.8 g three times. Subsequently, 26.4 g of ethyl acetate and 79.2 g of pure water were further added, and sodium hydrogen carbonate was added for neutralization. After neutralization, the salt was removed by filtration, 0.70 g of activated carbon (brand: special white birch dry product, Nippon Enviro Chemical) was added to the filtrate, and the mixture was stirred at room temperature and filtered. After washing the obtained solution twice with 66 g of pure water, the solvent was removed by concentration under reduced pressure, and 79.2 g of THF and 158 g of IPA were added and heated at 50 ° C., and the crystals were precipitated by cooling with ice and filtered. Crystals were collected. To the obtained crystals, 46.2 g of THF and 92.4 g of MeOH were added and heated at 50 ° C., and the crystals were precipitated by cooling with ice, followed by filtration and drying to obtain 8.92 g of RM8 (yield: 61%) , Properties: white crystals).
1 H-NMR (400 MHz) in CDCl3: 2.02-1.87 ppm (m, 8H), 2.67-2.60 ppm (m, 2H), 3.15-3.08 ppm (m, 2H), 4.13-4.02 ppm (m, 4H), 4.65-4.60 ppm (m, 2H), 5.66 ppm (s, 2H), 6.25 ppm (d, J = 2.4 Hz, 2H), 6.94 ppm (d, J = 8.8 Hz, 2H), 6.99 ppm (t, J = 8.6 Hz, 1H) 7.28-7.22 ppm (m, 2H), 7.44 ppm (d, J = 8.8 Hz, 2H)
マグネチックスターラーを備えた300mL四口フラスコに、DMF50.0g中、4,4’-ビフェノール20.0g(107mmol)と炭酸カリウム44.6g(3.0eq)、ヨウ化カリウム1.82g(0.1eq)を仕込み100℃に加熱し、DMF10.0gで希釈した2-ブロモメチル-1,3-ジオキソラン39.8g(2.2eq)を滴下し、同温度で6時間撹拌した。6時間後更に2-ブロモメチル-1,3-ジオキソラン5.38g(0.3eq)を追加し、18時間撹拌した。反応終了後、反応液を純水400gに加えて結晶を析出させ、ろ過し、ろ物をMeOH60.0gでスラリー洗浄し、再度ろ過することで白色固体を得た。得られた白色固体をTHF500gに懸濁させ、活性炭(銘柄:特製白鷺dry品 日本エンバイロケミカル製)1.00gを添加し、60℃で30分撹拌後、熱時ろ過(45℃)した。ろ液が冷えた結果、白色結晶が析出したため、ろ過乾燥することでRM9-A 13.0gを得た(収率:34%、性状:白色固体)。
1H-NMR(400MHz) in DMSO-d6: 3.85-3.93 ppm(m, 4H), 3.95-3.99 ppm(m, 4H), 4.03 ppm(d, J=4.0 Hz, 4H), 5.21 ppm(t, J=4.0 Hz, 2H), 7.01 ppm(d, J= 8.8 Hz, 4H), 7.53 ppm(d, J= 8.4 Hz, 4H) <Synthesis of RM9-A>
In a 300 mL four-necked flask equipped with a magnetic stirrer, 20.0 g (4,7 ') of 4,4′-biphenol, 44.6 g (3.0 eq) of potassium carbonate, and 1.82 g (0. 1 eq) was charged and heated to 100 ° C., 39.8 g (2.2 eq) of 2-bromomethyl-1,3-dioxolane diluted with 10.0 g of DMF was added dropwise, and the mixture was stirred at the same temperature for 6 hours. After 6 hours, 5.38 g (0.3 eq) of 2-bromomethyl-1,3-dioxolane was further added and stirred for 18 hours. After completion of the reaction, the reaction solution was added to 400 g of pure water to precipitate crystals, filtered, and the filtrate was slurry washed with 60.0 g of MeOH and filtered again to obtain a white solid. The obtained white solid was suspended in 500 g of THF, and 1.00 g of activated carbon (brand: special white rice dry product, Nippon Enviro Chemical) was added, stirred at 60 ° C. for 30 minutes, and then filtered while hot (45 ° C.). As a result of the cooling of the filtrate, white crystals were precipitated, and 13.0 g of RM9-A was obtained by filtration and drying (yield: 34%, property: white solid).
1 H-NMR (400 MHz) in DMSO-d6: 3.85-3.93 ppm (m, 4H), 3.95-3.99 ppm (m, 4H), 4.03 ppm (d, J = 4.0 Hz, 4H), 5.21 ppm (t, J = 4.0 Hz, 2H), 7.01 ppm (d, J = 8.8 Hz, 4H), 7.53 ppm (d, J = 8.4 Hz, 4H)
マグネチックスターラーを備えた300mL四口フラスコに、THF99.5g中、上記で得られた化合物(RM9-A)9.95g(27.8mmol)、2-(ブロモメチル)アクリル酸エチル11.8g(2.2eq)、塩化錫12.6g(2.4eq)、10wt%塩酸水溶液34.8gを仕込み、60℃にて1.5時間撹拌した。1.5時間後、20wt%塩酸水溶液9.95gを追加した後、更に21時間攪拌し、反応を完結させた。その後、THFを減圧留去し、酢酸エチル199gを加え、水相を除去した。次に、有機層を純水59.7gで2回洗浄した。有機相を回収し、酢酸エチルを減圧留去した後、THF149gを加えて還流攪拌した。続いて、活性炭(銘柄:特製白鷺dry品 日本エンバイロケミカル製)0.48gを加え1時間撹拌し、硫酸マグネシウムで脱水処理した後、これをろ過し、均一のろ液を得た。続いて、これを減圧濃縮しTHF量を79.6gとし、55℃にてMeOH159gを加えた後、暫く氷冷攪拌した。これにより析出した結晶をろ過乾燥し、RM9 8.4gを得た(収率:74%、性状:白色結晶)。
1H-NMR(400MHz) in DMSO-d6: 2.82-2.89 ppm(m, 2H), 3.10-3.18 ppm(m, 2H), 4.14 ppm(dd, J=5.4 Hz, J=11.0 Hz, 2H), 4.25 ppm(dd, J=2.6Hz, J=11.0 Hz, 2H), 5.78-5.79 ppm(m, 2H), 6.10-6.08 ppm(m, 2H), 7.00 ppm(d, J=8.4 Hz, 4H), 7.55 ppm(d, J=8.4 Hz) <Synthesis of RM9>
To a 300 mL four-necked flask equipped with a magnetic stirrer, in 99.5 g of THF, 9.95 g (27.8 mmol) of the compound (RM9-A) obtained above, 11.8 g of ethyl 2- (bromomethyl) acrylate (2 .2 eq), 12.6 g (2.4 eq) of tin chloride, and 34.8 g of a 10 wt% aqueous hydrochloric acid solution were added and stirred at 60 ° C. for 1.5 hours. After 1.5 hours, 9.95 g of a 20 wt% hydrochloric acid aqueous solution was added, and the mixture was further stirred for 21 hours to complete the reaction. Thereafter, THF was distilled off under reduced pressure, 199 g of ethyl acetate was added, and the aqueous phase was removed. Next, the organic layer was washed twice with 59.7 g of pure water. The organic phase was recovered, and ethyl acetate was distilled off under reduced pressure, and then 149 g of THF was added and stirred under reflux. Subsequently, 0.48 g of activated carbon (brand: special white birch dry product manufactured by Nippon Enviro Chemical) was added and stirred for 1 hour, dehydrated with magnesium sulfate, and then filtered to obtain a uniform filtrate. Subsequently, this was concentrated under reduced pressure to make the amount of THF 79.6 g, 159 g of MeOH was added at 55 ° C., and the mixture was stirred for a while on ice. The crystals thus precipitated were filtered and dried to obtain 8.4 g of RM9 (yield: 74%, property: white crystals).
1 H-NMR (400 MHz) in DMSO-d6: 2.82-2.89 ppm (m, 2H), 3.10-3.18 ppm (m, 2H), 4.14 ppm (dd, J = 5.4 Hz, J = 11.0 Hz, 2H), 4.25 ppm (dd, J = 2.6Hz, J = 11.0 Hz, 2H), 5.78-5.79 ppm (m, 2H), 6.10-6.08 ppm (m, 2H), 7.00 ppm (d, J = 8.4 Hz, 4H) 7.55 ppm (d, J = 8.4 Hz)
マグネチックスターラーを備えた200mL四口フラスコに、NMP20.0g中、4,4’-ビフェノール10.0g(53.7mmol)、4-クロロブチルアルデヒドジメチルアセタール18.4g(2.2eq)、炭酸カリウム22.3g(3.0eq)、ヨウ化カリウム1.78g(0.2eq)を仕込み、80℃にて3時間攪拌した。その後、4-クロロブチルアルデヒドジメチルアセタール2.45g(0.3eq)を追加し、更に16時間攪拌した。反応後、反応液を酢酸エチル50.0gで希釈し、無機塩をろ過した後、ろ液を酢酸エチル50.0gで希釈し、これを50℃にて純水50.0gで3回洗浄した。その後、この有機相を硫酸ナトリウムで脱水処理し、総重量68.0gまで減圧濃縮し、析出した結晶をろ過した。粗物にTHF5.0g及びMeOH20.0gを加え50℃にて溶解させた後、冷却し、暫く攪拌した。析出した結晶をろ過乾燥し、RM10-A 15.8gを得た(収率:70%、性状:白色固体)。
1H-NMR(400MHz) in DMSO-d6: 1.66-1.75 ppm(m, 8H), 3.24 ppm(s, 12H), 4.00 ppm(t, J=6.2 Hz, 4H), 4.42 ppm(t, J=5.2 Hz, 2H), 6.97 ppm(d, J=8.8 Hz, 4H), 7.52 ppm(d, J=8.4 Hz, 4H) <Synthesis of RM10-A>
In a 200 mL four-necked flask equipped with a magnetic stirrer, 10.0 g (53.7 mmol) of 4,4′-biphenol, 18.4 g (2.2 eq) of 4-chlorobutyraldehyde dimethylacetal in 20.0 g of NMP, potassium carbonate 22.3 g (3.0 eq) and 1.78 g (0.2 eq) of potassium iodide were charged and stirred at 80 ° C. for 3 hours. Thereafter, 2.45 g (0.3 eq) of 4-chlorobutyraldehyde dimethyl acetal was added, and the mixture was further stirred for 16 hours. After the reaction, the reaction solution was diluted with 50.0 g of ethyl acetate, the inorganic salt was filtered off, and the filtrate was diluted with 50.0 g of ethyl acetate, which was washed 3 times with 50.0 g of pure water at 50 ° C. . Thereafter, this organic phase was dehydrated with sodium sulfate, concentrated under reduced pressure to a total weight of 68.0 g, and the precipitated crystals were filtered. To the crude product, 5.0 g of THF and 20.0 g of MeOH were added and dissolved at 50 ° C., then cooled and stirred for a while. The precipitated crystals were filtered and dried to obtain 15.8 g of RM10-A (yield: 70%, property: white solid).
1 H-NMR (400 MHz) in DMSO-d6: 1.66-1.75 ppm (m, 8H), 3.24 ppm (s, 12H), 4.00 ppm (t, J = 6.2 Hz, 4H), 4.42 ppm (t, J = 5.2 Hz, 2H), 6.97 ppm (d, J = 8.8 Hz, 4H), 7.52 ppm (d, J = 8.4 Hz, 4H)
マグネチックスターラーを備えた500mL四口フラスコに、THF56.4g中、上記で得られた化合物(RM10-A)14.8g(35.4mmol)、2-(ブロモメチル)アクリル酸エチル15.0g(2.2eq)、塩化錫16.1g(2.4eq)、2,6-ジ-tert-ブチル-p-クレゾール0.39g(5mol%)、20wt%HCl水溶液51.8gを仕込み、60℃に3時間攪拌した。反応後、反応液を減圧濃縮し、純水148gを加えた後、析出した結晶をろ過し、純水148gで2回洗浄した。続いて、この結晶にTHF118g及びMeOH118gを加え50℃にて溶解させた後、室温まで放冷し暫く攪拌した。これにより得られた結晶をろ過するこで、粗物を得た。更に、この粗物にTHF237g及びIPA237gを加え60℃にて溶解させた後、室温まで冷却し暫く攪拌した。これにより析出した結晶をろ過し、THF74.0gで3回洗浄した後、減圧乾燥し、RM10 7.20gを得た(収率:44%、性状:白色結晶)。
1H-NMR(400MHz) in DMSO-d6: 1.75-1.85 ppm(m, 8H), 2.60-2.68 ppm(m, 2H), 3.08-3.15 ppm(m, 2H), 4.03 ppm(t, J=5.2 Hz, 4H), 4.61-4.67 ppm(m, 2H) 5.72-5.73 ppm(m, 2H), 6.04-6.05 ppm(m, 2H), 6.98 ppm(d, J=8.8 Hz, 4H), 7.52 ppm(d, J=8.8 Hz, 4H) <Synthesis of RM10>
In a 500 mL four-necked flask equipped with a magnetic stirrer, 14.8 g (35.4 mmol) of the compound (RM10-A) obtained above in 56.4 g of THF, 15.0 g of ethyl 2- (bromomethyl) acrylate (2 .2 eq), 16.1 g (2.4 eq) of tin chloride, 0.39 g (5 mol%) of 2,6-di-tert-butyl-p-cresol, and 51.8 g of 20 wt% HCl aqueous solution, Stir for hours. After the reaction, the reaction solution was concentrated under reduced pressure, 148 g of pure water was added, and the precipitated crystals were filtered and washed twice with 148 g of pure water. Subsequently, 118 g of THF and 118 g of MeOH were added to the crystals and dissolved at 50 ° C., then allowed to cool to room temperature and stirred for a while. The resulting crystals were filtered to obtain a crude product. Further, 237 g of THF and 237 g of IPA were added to this crude product and dissolved at 60 ° C., and then cooled to room temperature and stirred for a while. The crystals thus precipitated were filtered, washed 3 times with 74.0 g of THF, and then dried under reduced pressure to obtain 7.20 g of RM10 (yield: 44%, property: white crystals).
1 H-NMR (400 MHz) in DMSO-d6: 1.75-1.85 ppm (m, 8H), 2.60-2.68 ppm (m, 2H), 3.08-3.15 ppm (m, 2H), 4.03 ppm (t, J = 5.2 Hz, 4H), 4.61-4.67 ppm (m, 2H) 5.72-5.73 ppm (m, 2H), 6.04-6.05 ppm (m, 2H), 6.98 ppm (d, J = 8.8 Hz, 4H), 7.52 ppm ( d, J = 8.8 Hz, 4H)
マグネチックスターラーを備えた200mL四口フラスコに、NMP20g中、F含有ターフェニル化合物(RM3-A)10.0g(35.7mmol)、ブロモアセトアルデヒドジメチルアセタール13.3g(2.2eq)、炭酸カリウム14.8g(3.0eq)、ヨウ化カリウム1.78g(0.30eq)を仕込み、100℃にて13時間攪拌した。13時間後、ブロモアセトアルデヒドジメチルアセタール4.82g(0.8eq)と炭酸カリウム4.93g(1.0eq)を追加して更に12時間攪拌した。これにより、反応終了したため、反応溶液をTHF100gで希釈し、無機塩をろ過した後、THFを減圧留去した。次に、反応液に純水200gを加え、析出した結晶をろ過した。続いて、得られた結晶をTHF100gに懸濁し、内温50℃にて溶解させた後、IPA200gを加え、氷冷攪拌した。これにより析出した結晶をろ過乾燥し、RM11-A 11.9gを得た(収率:73%、性状:薄茶色結晶)。
1H-NMR(400MHz) in DMSO-d6: 3.58-3.36 ppm(m, 12H), 4.04 ppm(d, J=5.2 Hz, 4H), 4.74-4.71 ppm(m, 2H), 7.10-7.06 ppm(m, 4H), 7.58-7.52 ppm(m, 5H), 7.70 ppm(d, J=8.8 Hz, 2H) <Synthesis of RM11-A>
In a 200 mL four-necked flask equipped with a magnetic stirrer, 10.0 g (35.7 mmol) of F-containing terphenyl compound (RM3-A), 13.3 g (2.2 eq) of bromoacetaldehyde dimethyl acetal, potassium carbonate 14 in 20 g of NMP .8 g (3.0 eq) and potassium iodide 1.78 g (0.30 eq) were charged and stirred at 100 ° C. for 13 hours. After 13 hours, 4.82 g (0.8 eq) of bromoacetaldehyde dimethyl acetal and 4.93 g (1.0 eq) of potassium carbonate were added, and the mixture was further stirred for 12 hours. Thereby, since the reaction was completed, the reaction solution was diluted with 100 g of THF, the inorganic salt was filtered, and THF was distilled off under reduced pressure. Next, 200 g of pure water was added to the reaction solution, and the precipitated crystals were filtered. Subsequently, the obtained crystals were suspended in 100 g of THF and dissolved at an internal temperature of 50 ° C., and then 200 g of IPA was added and stirred on ice. The crystals thus precipitated were filtered and dried to obtain 11.9 g of RM11-A (yield: 73%, property: light brown crystals).
1 H-NMR (400 MHz) in DMSO-d 6 : 3.58-3.36 ppm (m, 12H), 4.04 ppm (d, J = 5.2 Hz, 4H), 4.74-4.71 ppm (m, 2H), 7.10-7.06 ppm (m, 4H), 7.58-7.52 ppm (m, 5H), 7.70 ppm (d, J = 8.8 Hz, 2H)
マグネチックスターラーを備えた500mL四口フラスコに、THF110g中、上記で得られた化合物(RM11-A)11.0g(24.2mmol)、2-(ブロモメチル)アクリル酸エチル10.3g(2.2eq)、塩化錫11.0g(2.4eq)、10wt%HCl水溶液38.6gを仕込み、内温40℃で18時間反応させた。18時間後、20wt%HCl水溶液11.0gを加え、更に6時間攪拌した。その後、2,6-ジ-tert-ブチル-p-クレゾール27mgを添加し、THFを減圧留去した後、純水110gを加え析出した結晶をろ過した。次に、得られた結晶をTHF1100gに懸濁し、60℃にて溶け残った不溶物をろ過した後、ろ液に活性炭(銘柄:特製白鷺dry品 日本エンバイロケミカル製)0.55gを加え、60℃にて30分程撹拌した。続いて、活性炭をろ過し、ろ液を減圧濃縮することでTHF110gまで減らした後、析出した結晶をろ過乾燥し、RM11 4.67gを得た(収率:39%, 性状:白色結晶)。
1H-NMR(400MHz) in DMSO-d6 : 2.86 ppm(d, J=17.6 Hz, 2H), 3.15 ppm(dd, J=8.2 Hz, 17.4 Hz, 2H), 4.17 ppm(dd, J=5.4 Hz, 11 Hz, 2H), 4.29 ppm(dd, J=2.6 Hz, 11 Hz, 2H), 4.99-4.96ppm(m, 2H), 5.79-5.78 ppm(m, 2H), 6.10-6.09 ppm(m, 2H), 7.01-7.04 ppm(m, 4H), 7.59-7.52 ppm(m, 5H), 7.71 ppm(d, J=8.8 Hz, 2H) <Synthesis of RM11>
In a 500 mL four-necked flask equipped with a magnetic stirrer, 11.0 g (24.2 mmol) of the compound (RM11-A) obtained above in 110 g of THF, 10.3 g (2.2 eq) of ethyl 2- (bromomethyl) acrylate. ), 11.0 g (2.4 eq) of tin chloride and 38.6 g of 10 wt% HCl aqueous solution were charged and reacted at an internal temperature of 40 ° C. for 18 hours. After 18 hours, 11.0 g of a 20 wt% aqueous HCl solution was added, and the mixture was further stirred for 6 hours. Thereafter, 27 mg of 2,6-di-tert-butyl-p-cresol was added, THF was distilled off under reduced pressure, 110 g of pure water was added, and the precipitated crystals were filtered. Next, after suspending the obtained crystal in 1100 g of THF and filtering insoluble matter remaining undissolved at 60 ° C., 0.55 g of activated carbon (brand: special white birch dry product manufactured by Nippon Enviro Chemical) was added to the filtrate. Stir at 30 ° C. for about 30 minutes. Subsequently, the activated carbon was filtered and the filtrate was concentrated under reduced pressure to reduce to 110 g of THF. Then, the precipitated crystals were filtered and dried to obtain 4.67 g of RM11 (yield: 39%, property: white crystals).
1 H-NMR (400 MHz) in DMSO-d6: 2.86 ppm (d, J = 17.6 Hz, 2H), 3.15 ppm (dd, J = 8.2 Hz, 17.4 Hz, 2H), 4.17 ppm (dd, J = 5.4 Hz) , 11 Hz, 2H), 4.29 ppm (dd, J = 2.6 Hz, 11 Hz, 2H), 4.99-4.96 ppm (m, 2H), 5.79-5.78 ppm (m, 2H), 6.10-6.09 ppm (m, 2H), 7.01-7.04 ppm (m, 4H), 7.59-7.52 ppm (m, 5H), 7.71 ppm (d, J = 8.8 Hz, 2H)
冷却管付き200mlナスフラスコに、F含有ターフェニル化合物(RM3-A)4.0g(14.3mmol)、4-ブロモブチル-1,3-ジオキソラン6.3g(2.1eq)、炭酸カリウム8.3g(4.0eq)、およびアセトン100mlを加えて混合物とし、還流条件下で24時間撹拌しながら反応させた。反応終了後、反応液を純水500mlに注ぎ、白色固体を得た。この白色固体を再結晶(ヘキサン/テトラヒドロフラン、5/1)で精製した後、RM12-A 5.9gを得た(収率:77%、性状:白色結晶)。
1H-NMR(400MHz) in CDCl3: 1.62 ppm (m, 4H), 1.77 ppm (m, 4H), 1.91 ppm (m, 4H), 3.87 ppm (m, 4H), 4.04 ppm (m, 8H), 4.90 ppm (m, 2H), 7.00 ppm (m, 4H), 7.50-7.80 ppm (m, 7H). <Synthesis of RM12-A>
In a 200 ml eggplant flask equipped with a condenser tube, 4.0 g (14.3 mmol) of F-containing terphenyl compound (RM3-A), 6.3 g (2.1 eq) of 4-bromobutyl-1,3-dioxolane, 8.3 g of potassium carbonate (4.0 eq) and 100 ml of acetone were added to form a mixture, and the mixture was allowed to react with stirring under reflux conditions for 24 hours. After completion of the reaction, the reaction solution was poured into 500 ml of pure water to obtain a white solid. The white solid was purified by recrystallization (hexane / tetrahydrofuran, 5/1) to obtain 5.9 g of RM12-A (yield: 77%, property: white crystals).
1 H-NMR (400 MHz) in CDCl 3 : 1.62 ppm (m, 4H), 1.77 ppm (m, 4H), 1.91 ppm (m, 4H), 3.87 ppm (m, 4H), 4.04 ppm (m, 8H) , 4.90 ppm (m, 2H), 7.00 ppm (m, 4H), 7.50-7.80 ppm (m, 7H).
冷却管付き100mlナスフラスコに、上記で得られた化合物(RM12-A)3.0g(5.6mmol)、2-(ブロモメチル)アクリル酸2.3g(2.5eq)、THF35ml、塩化錫(無水物)2.6g(2.5eq)、および10%HCl水溶液11mlを加えて混合物とし、70℃で20時間撹拌して反応させた。反応終了後、反応液を純水500mlに注ぎ、白色結晶を得た。得られた白色結晶を再結晶(ヘキサン/クロロホルム、5/1)で精製した後、RM12を2.4g得た(収率:73%、性状:白色結晶)。
1H-NMR(400MHz) in CDCl3: 1.50-1.90 ppm (m, 12H), 2.60 ppm (m, 2H),3.10 ppm (m, 2H), 4.03 ppm (m, 4H), 4.58 ppm (m, 2H), 5.65 ppm (m, 2H), 6.23 ppm (m, 2H), 6.94 ppm (m, 4H), 7.50-7.80 ppm (m, 7H). <Synthesis of RM12>
In a 100 ml eggplant flask equipped with a condenser tube, 3.0 g (5.6 mmol) of the compound (RM12-A) obtained above, 2.3 g (2.5 eq) of 2- (bromomethyl) acrylic acid, 35 ml of THF, tin chloride (anhydrous) Product) 2.6 g (2.5 eq) and 10% HCl aqueous solution 11 ml were added to make a mixture, and the mixture was stirred at 70 ° C. for 20 hours to be reacted. After completion of the reaction, the reaction solution was poured into 500 ml of pure water to obtain white crystals. After the obtained white crystals were purified by recrystallization (hexane / chloroform, 5/1), 2.4 g of RM12 was obtained (yield: 73%, property: white crystals).
1 H-NMR (400 MHz) in CDCl 3 : 1.50-1.90 ppm (m, 12H), 2.60 ppm (m, 2H), 3.10 ppm (m, 2H), 4.03 ppm (m, 4H), 4.58 ppm (m, 2H), 5.65 ppm (m, 2H), 6.23 ppm (m, 2H), 6.94 ppm (m, 4H), 7.50-7.80 ppm (m, 7H).
BODA(2.00g、8.0mmol)、DA-2(2.40g、6.0mmol)、DA-4(0.94g、6.2mmol)、DA-6(1.77g、3.8mmol)、DA-8(1.32g、4.0mmol)、をNMP(32.2g)中で溶解し、60℃で3時間反応させたのち、CBDA(2.27g、11.6mmol)とNMP(10.7g)を加え、室温で10時間反応させポリアミック酸溶液を得た。
このポリアミック酸溶液(50g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(5.7g)、およびピリジン(2.9g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(700ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(A)-1を得た。このポリイミドのイミド化率は60%であり、数平均分子量は12000、重量平均分子量は33000であった。
得られたポリイミド粉末(A)-1(6.0g)にNMP(44.0g)を加え、50℃にて5時間攪拌して溶解させた。この溶液に3AMP(1wt%NMP溶液)6.0g、NMP(14.0g)、BCS(30.0g)を加え、室温で5時間攪拌することにより液晶配向剤D1を得た。 <Synthesis Example 13 -Synthesis of Liquid Crystal Alignment Agent D1->
BODA (2.00 g, 8.0 mmol), DA-2 (2.40 g, 6.0 mmol), DA-4 (0.94 g, 6.2 mmol), DA-6 (1.77 g, 3.8 mmol), DA-8 (1.32 g, 4.0 mmol) was dissolved in NMP (32.2 g), reacted at 60 ° C. for 3 hours, and then CBDA (2.27 g, 11.6 mmol) and NMP (10. 7 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (5.7 g) and pyridine (2.9 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -1. The imidation ratio of this polyimide was 60%, the number average molecular weight was 12000, and the weight average molecular weight was 33000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -1 (6.0 g), and dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D1 was obtained by stirring at room temperature for 5 hours.
BODA(2.00g、8.0mmol)、DA-8(3.30g、10.0mmol)、DA-2(4.00g、10.0mmol)をNMP(34.8g)中で溶解し、60℃で3時間反応させたのち、CBDA(2.27g、11.6mmol)とNMP(11.6g)を加え、室温で10時間反応させポリアミック酸溶液を得た。
このポリアミック酸溶液(50g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(5.3g)、およびピリジン(2.7g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(700ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(A)-2を得た。このポリイミドのイミド化率は60%であり、数平均分子量は15000、重量平均分子量は41000であった。
得られたポリイミド粉末(A)-2(6.0g)にNMP(44.0g)を加え、50℃にて5時間攪拌して溶解させた。この溶液に3AMP(1wt%NMP溶液)6.0g、NMP(14.0g)、BCS(30.0g)を加え、室温で5時間攪拌することにより液晶配向剤D2を得た。 <Synthesis Example 14 -Synthesis of Liquid Crystal Alignment Agent D2->
BODA (2.00 g, 8.0 mmol), DA-8 (3.30 g, 10.0 mmol), DA-2 (4.00 g, 10.0 mmol) were dissolved in NMP (34.8 g) at 60 ° C. Then, CBDA (2.27 g, 11.6 mmol) and NMP (11.6 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (5.3 g) and pyridine (2.7 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -2. The imidation ratio of this polyimide was 60%, the number average molecular weight was 15000, and the weight average molecular weight was 41000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -2 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. To this solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g), and BCS (30.0 g) were added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D2.
BODA(2.00g、8.0mmol)、DA-6(4.67g、10.0mmol)、DA-2(4.00g、10.0mmol)をNMP(38.9g)中で溶解し、60℃で3時間反応させたのち、CBDA(2.27g、11.6mmol)とNMP(13.0g)を加え、室温で10時間反応させポリアミック酸溶液を得た。
このポリアミック酸溶液(50g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(3.1g)、およびピリジン(12.1g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(700ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(A)-3を得た。このポリイミドのイミド化率は60%であり、数平均分子量は15000、重量平均分子量は36000であった。
得られたポリイミド粉末(A)-3(6.0g)にNMP(44.0g)を加え、50℃にて5時間攪拌して溶解させた。この溶液に3AMP(1wt%NMP溶液)6.0g、NMP(14.0g)、BCS(30.0g)を加え、室温で5時間攪拌することにより液晶配向剤D3を得た。 <Synthesis Example 15 -Synthesis of Liquid Crystal Alignment Agent D3->
BODA (2.00 g, 8.0 mmol), DA-6 (4.67 g, 10.0 mmol), DA-2 (4.00 g, 10.0 mmol) were dissolved in NMP (38.9 g) at 60 ° C. Then, CBDA (2.27 g, 11.6 mmol) and NMP (13.0 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (3.1 g) and pyridine (12.1 g) were added as an imidization catalyst, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -3. The imidation ratio of this polyimide was 60%, the number average molecular weight was 15000, and the weight average molecular weight was 36000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -3 (6.0 g) and dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D3 was obtained by stirring at room temperature for 5 hours.
BODA(2.00g、8.0mmol)、DA-7(2.64g、10.0mmol)、DA-2(4.00g、10.0mmol)をNMP(32.8g)中で溶解し、60℃で3時間反応させたのち、CBDA(2.27g、11.6mmol)とNMP(10.9g)を加え、室温で10時間反応させポリアミック酸溶液を得た。
このポリアミック酸溶液(50g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(3.7g)、およびピリジン(14.4g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(700ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(A)-4を得た。このポリイミドのイミド化率は60%であり、数平均分子量は25000、重量平均分子量は45000であった。
得られたポリイミド粉末(A)-4(6.0g)にNMP(44.0g)を加え、50℃にて5時間攪拌して溶解させた。この溶液に3AMP(1wt%NMP溶液)6.0g、NMP(14.0g)、BCS(30.0g)を加え、室温で5時間攪拌することにより液晶配向剤D4を得た。 <Synthesis Example 16 -Synthesis of Liquid Crystal Alignment Agent D4->
BODA (2.00 g, 8.0 mmol), DA-7 (2.64 g, 10.0 mmol), DA-2 (4.00 g, 10.0 mmol) were dissolved in NMP (32.8 g) at 60 ° C. Then, CBDA (2.27 g, 11.6 mmol) and NMP (10.9 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (3.7 g) and pyridine (14.4 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -4. The imidation ratio of this polyimide was 60%, the number average molecular weight was 25000, and the weight average molecular weight was 45000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -4 (6.0 g) and dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D4 was obtained by stirring at room temperature for 5 hours.
TCA(1.35g、6.0mmol)、DA-1(2.28g、6.0mmol)、DA-8(2.97g、9.0mmol)をNMP(24.9g)中で溶解し、80℃で3時間反応させたのち、CBDA(1.74g、8.9mmol)とNMP(8.3g)を加え、室温で10時間反応させポリアミック酸溶液を得た。
このポリアミック酸溶液(36g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(4.0g)、およびピリジン(2.1g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(700ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(A)-5を得た。このポリイミドのイミド化率は60%であり、数平均分子量は20000、重量平均分子量は43000であった。
得られたポリイミド粉末(A)-5(6.0g)にNMP(44.0g)を加え、50℃にて5時間攪拌して溶解させた。この溶液に3AMP(1wt%NMP溶液)6.0g、NMP(14.0g)、BCS(30.0g)を加え、室温で5時間攪拌することにより液晶配向剤D5を得た。 <Synthesis Example 17 -Synthesis of Liquid Crystal Alignment Agent D5->
TCA (1.35 g, 6.0 mmol), DA-1 (2.28 g, 6.0 mmol), DA-8 (2.97 g, 9.0 mmol) were dissolved in NMP (24.9 g) at 80 ° C. Then, CBDA (1.74 g, 8.9 mmol) and NMP (8.3 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (36 g) and diluting to 6% by mass, acetic anhydride (4.0 g) and pyridine (2.1 g) were added as an imidization catalyst, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -5. The imidation ratio of this polyimide was 60%, the number average molecular weight was 20000, and the weight average molecular weight was 43,000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -5 (6.0 g) and dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D5 was obtained by stirring at room temperature for 5 hours.
BODA(2.00g、8.0mmol)、DA-8(4.63g、14.0mmol)、DA-3(2.61g、6.0mmol)をNMP(34.5g)中で溶解し、60℃で3時間反応させたのち、CBDA(2.27g、11.6mmol)とNMP(11.5g)を加え、室温で10時間反応させポリアミック酸溶液を得た。
このポリアミック酸溶液(50g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(5.3g)、およびピリジン(2.7g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(700ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(A)-6を得た。このポリイミドのイミド化率は60%であり、数平均分子量は17000、重量平均分子量は35000であった。
得られたポリイミド粉末(A)-6(6.0g)にNMP(44.0g)を加え、50℃にて5時間攪拌して溶解させた。この溶液に3AMP(1wt%NMP溶液)6.0g、NMP(14.0g)、BCS(30.0g)を加え、室温で5時間攪拌することにより液晶配向剤D6を得た。 <Synthesis Example 18 -Synthesis of Liquid Crystal Alignment Agent D6->
BODA (2.00 g, 8.0 mmol), DA-8 (4.63 g, 14.0 mmol), DA-3 (2.61 g, 6.0 mmol) were dissolved in NMP (34.5 g) at 60 ° C. Then, CBDA (2.27 g, 11.6 mmol) and NMP (11.5 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (5.3 g) and pyridine (2.7 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -6. The imidation ratio of this polyimide was 60%, the number average molecular weight was 17000, and the weight average molecular weight was 35000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -6 (6.0 g), and dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D6 was obtained by stirring at room temperature for 5 hours.
BODA(1.30g、5.2mmol)、DA-9(2.09g、3.9mmol)、DA-8(3.00g、9.1mmol)をNMP(23.5g)中で溶解し、60℃で3時間反応させたのち、CBDA(1.43g、7.3mmol)とNMP(7.8g)を加え、室温で10時間反応させポリアミック酸溶液を得た。
このポリアミック酸溶液(36g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(3.6g)、およびピリジン(1.9g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(700ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(A)-7を得た。このポリイミドのイミド化率は60%であり、数平均分子量は16000、重量平均分子量は36000であった。
得られたポリイミド粉末(A)-7(6.0g)にNMP(44.0g)を加え、50℃にて5時間攪拌して溶解させた。この溶液に3AMP(1wt%NMP溶液)6.0g、NMP(14.0g)、BCS(30.0g)を加え、室温で5時間攪拌することにより液晶配向剤D7を得た。 <Synthesis Example 19 -Synthesis of Liquid Crystal Alignment Agent D7->
BODA (1.30 g, 5.2 mmol), DA-9 (2.09 g, 3.9 mmol), DA-8 (3.00 g, 9.1 mmol) were dissolved in NMP (23.5 g) at 60 ° C. Then, CBDA (1.43 g, 7.3 mmol) and NMP (7.8 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (36 g) and diluting to 6% by mass, acetic anhydride (3.6 g) and pyridine (1.9 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -7. The imidation ratio of this polyimide was 60%, the number average molecular weight was 16000, and the weight average molecular weight was 36000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -7 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D7 was obtained by stirring at room temperature for 5 hours.
BODA(2.00g、8.0mmol)、DA-8(3.96g、12.0mmol)、DA-1(3.04g、8.0mmol)をNMP(33.9g)中で溶解し、60℃で3時間反応させたのち、CBDA(2.27g、11.6mmol)とNMP(11.3g)を加え、室温で10時間反応させポリアミック酸溶液を得た。
このポリアミック酸溶液(50g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(5.4g)、およびピリジン(2.8g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(700ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(A)-8を得た。このポリイミドのイミド化率は60%であり、数平均分子量は18000、重量平均分子量は40000であった。
得られたポリイミド粉末(A)-8(6.0g)にNMP(44.0g)を加え、50℃にて5時間攪拌して溶解させた。この溶液に3AMP(1wt%NMP溶液)6.0g、NMP(14.0g)、BCS(30.0g)を加え、室温で5時間攪拌することにより液晶配向剤D8を得た。 <Synthesis Example 20 -Synthesis of Liquid Crystal Alignment Agent D8->
BODA (2.00 g, 8.0 mmol), DA-8 (3.96 g, 12.0 mmol), DA-1 (3.04 g, 8.0 mmol) were dissolved in NMP (33.9 g) at 60 ° C. Then, CBDA (2.27 g, 11.6 mmol) and NMP (11.3 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (5.4 g) and pyridine (2.8 g) were added as imidation catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -8. The imidation ratio of this polyimide was 60%, the number average molecular weight was 18000, and the weight average molecular weight was 40000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -8 (6.0 g), and dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D8 was obtained by stirring at room temperature for 5 hours.
BODA(2.00g、8.0mmol)、DA-1(2.28g、6.0mmol)、DA-4(1.22g、8.0mmol)、DA-5(1.45g、6.0mmol)をNMP(29.5g)中で溶解し、60℃で3時間反応させたのち、PMDA(2.53g、11.6mmol)とNMP(9.5g)を加え、室温で10時間反応させポリアミック酸溶液を得た。
このポリアミック酸溶液(50g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(6.4g)、およびピリジン(3.3g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(700ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(A)-9を得た。このポリイミドのイミド化率は60%であり、数平均分子量は10000、重量平均分子量は31000であった。
得られたポリイミド粉末(A)-9(6.0g)にNMP(44.0g)を加え、50℃にて5時間攪拌して溶解させた。この溶液に3AMP(1wt%NMP溶液)6.0g、NMP(14.0g)、BCS(30.0g)を加え、室温で5時間攪拌することにより液晶配向剤D9を得た。 <Synthesis Example 21 -Synthesis of Liquid Crystal Alignment Agent D9->
BODA (2.00 g, 8.0 mmol), DA-1 (2.28 g, 6.0 mmol), DA-4 (1.22 g, 8.0 mmol), DA-5 (1.45 g, 6.0 mmol). After dissolving in NMP (29.5 g) and reacting at 60 ° C. for 3 hours, PMDA (2.53 g, 11.6 mmol) and NMP (9.5 g) were added, and the mixture was reacted at room temperature for 10 hours to obtain a polyamic acid solution Got.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (6.4 g) and pyridine (3.3 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -9. The imidation ratio of this polyimide was 60%, the number average molecular weight was 10,000, and the weight average molecular weight was 31000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -9 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D9 was obtained by stirring at room temperature for 5 hours.
合成例20で得られた液晶配向剤D8 7.0gに対して、合成例21で得られた液晶配向剤D9 3.0gを加え、室温で5時間攪拌することにより、液晶配向剤D10を得た。 <Synthesis Example 22 -Synthesis of Liquid Crystal Alignment Agent D10->
By adding 3.0 g of the liquid crystal aligning agent D9 obtained in Synthesis Example 21 to 7.0 g of the liquid crystal aligning agent D8 obtained in Synthesis Example 20, the liquid crystal aligning agent D10 is obtained by stirring at room temperature for 5 hours. It was.
BODA(2.00g、8.0mmol)、DA-1(1.52g、4.0mmol)、DA-4(1.22g、8.0mmol)、DA-8(2.64g、8.0mmol)をNMP(20.7g)中で溶解し、60℃で3時間反応させたのち、PMDA(2.53g、11.6mmol)とNMP(9.9g)を加え、室温で10時間反応させポリアミック酸溶液を得た。
このポリアミック酸溶液(50g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(6.1g)、およびピリジン(3.2g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(700ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(A)-10を得た。このポリイミドのイミド化率は60%であり、数平均分子量は9000、重量平均分子量は25000であった。
得られたポリイミド粉末(A)-10(6.0g)にNMP(44.0g)を加え、50℃にて5時間攪拌して溶解させた。この溶液に3AMP(1wt%NMP溶液)6.0g、NMP(14.0g)、BCS(30.0g)を加え、室温で5時間攪拌することにより液晶配向剤D11を得た。 <Synthesis Example 23 -Synthesis of Liquid Crystal Alignment Agent D11->
BODA (2.00 g, 8.0 mmol), DA-1 (1.52 g, 4.0 mmol), DA-4 (1.22 g, 8.0 mmol), DA-8 (2.64 g, 8.0 mmol). After dissolving in NMP (20.7 g) and reacting at 60 ° C. for 3 hours, PMDA (2.53 g, 11.6 mmol) and NMP (9.9 g) were added, and the mixture was reacted at room temperature for 10 hours to obtain a polyamic acid solution Got.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (6.1 g) and pyridine (3.2 g) were added as an imidization catalyst, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -10. The imidation ratio of this polyimide was 60%, the number average molecular weight was 9000, and the weight average molecular weight was 25000.
NMP (44.0 g) was added to the resulting polyimide powder (A) -10 (6.0 g), and dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D11 was obtained by stirring at room temperature for 5 hours.
合成例20で得られた液晶配向剤D8 7.0gに対して、合成例23で得られた液晶配向剤D11 3.0gを加え、室温で5時間攪拌することにより、液晶配向剤D12を得た。 <Synthesis Example 24 -Synthesis of Liquid Crystal Alignment Agent D12->
3.0 g of the liquid crystal aligning agent D11 obtained in Synthesis Example 23 is added to 7.0 g of the liquid crystal aligning agent D8 obtained in Synthesis Example 20, and the liquid crystal aligning agent D12 is obtained by stirring at room temperature for 5 hours. It was.
BODA(3.75g、15.0mmol)、DA-1(3.81g、10.0mmol)、DA-4(1.52g、10.0mmol)をNMP(30.0g)中で溶解し、80℃で5時間反応させたのち、CBDA(0.94g、4.8mmol)とNMP(10.0g)を加え、40℃で10時間反応させポリアミック酸溶液を得た。
このポリアミック酸溶液(50g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(4.7g)、およびピリジン(3.7g)を加え、80℃で3時間反応させた。この反応溶液をメタノール(700ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(A)-11を得た。このポリイミドのイミド化率は55%であり、数平均分子量は20000、重量平均分子量は40000であった。
得られたポリイミド粉末(A)-11(6.0g)にNMP(44.0g)を加え、50℃にて5時間攪拌して溶解させた。この溶液に3AMP(1wt%NMP溶液)6.0g、NMP(14.0g)、BCS(30.0g)を加え、室温で5時間攪拌することにより液晶配向剤D13を得た。 <Synthesis Example 25 -Synthesis of Liquid Crystal Alignment Agent D13->
BODA (3.75 g, 15.0 mmol), DA-1 (3.81 g, 10.0 mmol), DA-4 (1.52 g, 10.0 mmol) were dissolved in NMP (30.0 g) and dissolved at 80 ° C. Then, CBDA (0.94 g, 4.8 mmol) and NMP (10.0 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (4.7 g) and pyridine (3.7 g) were added as imidation catalysts, and the mixture was reacted at 80 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -11. The imidation ratio of this polyimide was 55%, the number average molecular weight was 20000, and the weight average molecular weight was 40000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -11 (6.0 g), and dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D13 was obtained by stirring at room temperature for 5 hours.
BODA(2.00g、8.0mmol)、DA-6(6.53g、14.0mmol)、DA-2(2.40g、6.0mmol)をNMP(26.4g)中で溶解し、60℃で3時間反応させたのち、CBDA(2.27g、11.6mmol)とNMP(13.2g)を加え、室温で10時間反応させポリアミック酸溶液を得た。このポリアミック酸溶液の数平均分子量は20000、重量平均分子量は40000であった。
このポリアミック酸溶液(30g)にNMP(40.0g)、BCS(30.0g)を加え、室温で5時間攪拌することにより液晶配向剤D14を得た。 <Synthesis Example 26 -Synthesis of Liquid Crystal Alignment Agent D14->
BODA (2.00 g, 8.0 mmol), DA-6 (6.53 g, 14.0 mmol), DA-2 (2.40 g, 6.0 mmol) were dissolved in NMP (26.4 g) at 60 ° C. Then, CBDA (2.27 g, 11.6 mmol) and NMP (13.2 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. The number average molecular weight of this polyamic acid solution was 20000, and the weight average molecular weight was 40000.
NMP (40.0g) and BCS (30.0g) were added to this polyamic acid solution (30g), and the liquid crystal aligning agent D14 was obtained by stirring at room temperature for 5 hours.
マグネチックスターラーを備えた300ml四口フラスコに、NMP18.1g中、RM1-A 9.0g(44.1mmol)を仕込み、NMP17.9gで共洗いした後、炭酸カリウム18.3g(3.0eq)を加え、NMP18.0gで共洗いした。これを80℃にて撹拌させながら、2-(2-ブロモエチル)-1,3-ジオキソラン17.6g(2.2eq)を30分間かけて滴下した後、18時間攪拌した。18時間後、更に2-(2-ブロモエチル)-1,3-ジオキソラン2.4g(0.3eq)を追加し、更に3.5時間反応させ、中間体の消失を確認した。反応終了後、室温にて反応液中に多量の水を加え、炭酸カリウムを溶解しながら目的物の結晶を析出させ、ろ過した。回収した結晶を純水でスラリー洗浄を2度行い、ろ過乾燥し、RM13-Aの粗物17.8gを得た(収率:100%、性状:薄茶色結晶)。
1H-NMR(400MHz) in DMSO-d6:7.57ppm(d, J=8.8Hz, 2H), 7.49ppm(dd, J=2.2 Hz, J=13.0Hz, 1H), 7.38ppm(d, J=10.0Hz, 1H), 7.21ppm(t, J=8.8Hz, 1H), 6.99ppm(d, J=8.4Hz, 2H), 5.02-4.99ppm(m, 2H), 4.18ppm(t, J=6.6Hz, 2H), 4.10ppm(t, J=6.6Hz, 2H), 3.94-3.91ppm(m, 4H), 3.82-3.78ppm(m, 4H), 2.09-2.02ppm(m, 4H). <Synthesis of RM13-A>
A 300 ml four-necked flask equipped with a magnetic stirrer was charged with 9.0 g (44.1 mmol) of RM1-A in 18.1 g of NMP, washed with 17.9 g of NMP, and then 18.3 g (3.0 eq) of potassium carbonate. And washed with 18.0 g of NMP. While stirring this at 80 ° C., 17.6 g (2.2 eq) of 2- (2-bromoethyl) -1,3-dioxolane was added dropwise over 30 minutes, and then stirred for 18 hours. After 18 hours, further 2.4 g (0.3 eq) of 2- (2-bromoethyl) -1,3-dioxolane was added, and the mixture was further reacted for 3.5 hours to confirm the disappearance of the intermediate. After completion of the reaction, a large amount of water was added to the reaction solution at room temperature, and crystals of the target product were precipitated while dissolving potassium carbonate, followed by filtration. The collected crystals were washed twice with pure water and washed with filtration, and dried by filtration to obtain 17.8 g of a crude product of RM13-A (yield: 100%, properties: light brown crystals).
1 H-NMR (400 MHz) in DMSO-d 6 : 7.57 ppm (d, J = 8.8 Hz, 2H), 7.49 ppm (dd, J = 2.2 Hz, J = 13.0 Hz, 1H), 7.38 ppm (d, J = 10.0Hz, 1H), 7.21ppm (t, J = 8.8Hz, 1H), 6.99ppm (d, J = 8.4Hz, 2H), 5.02-4.99ppm (m, 2H), 4.18ppm (t, J = 6.6Hz, 2H), 4.10ppm (t, J = 6.6Hz, 2H), 3.94-3.91ppm (m, 4H), 3.82-3.78ppm (m, 4H), 2.09-2.02ppm (m, 4H).
マグネチックスターラーを備えた500ml四口フラスコに、THF135g中、RM13-A 15.0g(37.1mmol)、塩化錫(II)無水物16.9g(2.4eq)、2-(ブロモメチル)アクリル酸エチル15.9g(2.2eq)を加えた後、20~30℃にて10wt%HCl水溶液52.5gを45分掛けて滴下した。その後、室温にて7日間攪拌し、原料及び中間体を消失させた。次に、反応液にトルエン300gを加える事で2相に分け、熱時分液(50℃)にて塩酸相を除去した。有機相は一旦フラスコに回収し、6wt%KOH水溶液300g、50℃攪拌状態のジャケット付セパラブルフラスコ中へ滴下した。途中で不溶物が界面に生じてきたため、6wt%KOH水溶液150gを追加した。次に、アルカリ相を除去した後、有機相を純水300gで3回洗浄した後、有機相を回収した。これに活性炭0.75g(銘柄:特製白鷺dry品 日本エンバイロケミカル製)、硫酸ナトリウム30.0g、THF105gを加え、室温にて30分攪拌した後、固液分離を行い、ろ液を回収した。これを濃縮乾固し、MeOH45.0gを加えた後、室温にて1時間スラリー洗浄した。これをろ過後、得られたろ物をMeOH7.5gで洗浄した後、減圧乾燥し、RM13 7.6gを得た(収率:45%、性状:白色結晶)。
1H-NMR(400MHz) in DMSO-d6: 7.59 ppm(d, J=8.8Hz, 2H), 7.51 ppm (dd, J=2.0 Hz, J=12.8Hz, 1H), 7.40 ppm(dd, J=1.6 Hz, J=8.0 Hz, 1H), 7.34 ppm(t, J=9.0 Hz, 1H), 7.01 ppm (d, J=8.8 Hz, 2H), 6.05ppm (dd, J=2.6 Hz, J=5.0Hz, 2H), 5.74ppm (d, J=2.0Hz, 2H), 4.81-4.75ppm(m, 2H), 4.20ppm(t, J=6.2Hz, 2H), 4.13ppm(t, J=6.2Hz, 2H), 3.21-3.12ppm(m, 2H), 2.79-2.71ppm(m, 2H), 2.17-2.08ppm(m,4H). <Synthesis of RM13>
In a 500 ml four-necked flask equipped with a magnetic stirrer, 15.0 g (37.1 mmol) of RM13-A, 16.9 g (2.4 eq) of tin (II) chloride anhydride, 2- (bromomethyl) acrylic acid in 135 g of THF After adding 15.9 g (2.2 eq) of ethyl, 52.5 g of 10 wt% aqueous HCl solution was added dropwise at 20-30 ° C. over 45 minutes. Then, it stirred at room temperature for 7 days and the raw material and the intermediate body were lose | disappeared. Next, 300 g of toluene was added to the reaction solution to separate it into two phases, and the hydrochloric acid phase was removed by hot separation (50 ° C.). The organic phase was once recovered in a flask and dropped into a jacketed separable flask with 300 g of 6 wt% KOH aqueous solution and stirred at 50 ° C. Since insoluble matter was generated at the interface, 150 g of 6 wt% KOH aqueous solution was added. Next, after removing the alkali phase, the organic phase was washed three times with 300 g of pure water, and then the organic phase was recovered. To this was added 0.75 g of activated carbon (brand: special white birch dry product manufactured by Nippon Enviro Chemical), 30.0 g of sodium sulfate, and 105 g of THF, and the mixture was stirred at room temperature for 30 minutes, followed by solid-liquid separation, and the filtrate was collected. This was concentrated to dryness, 45.0 g of MeOH was added, and the slurry was washed at room temperature for 1 hour. After filtration, the obtained filtrate was washed with 7.5 g of MeOH and then dried under reduced pressure to obtain 7.6 g of RM13 (yield: 45%, property: white crystals).
1 H-NMR (400 MHz) in DMSO-d 6 : 7.59 ppm (d, J = 8.8 Hz, 2H), 7.51 ppm (dd, J = 2.0 Hz, J = 12.8 Hz, 1H), 7.40 ppm (dd, J = 1.6 Hz, J = 8.0 Hz, 1H), 7.34 ppm (t, J = 9.0 Hz, 1H), 7.01 ppm (d, J = 8.8 Hz, 2H), 6.05 ppm (dd, J = 2.6 Hz, J = 5.0Hz, 2H), 5.74ppm (d, J = 2.0Hz, 2H), 4.81-4.75ppm (m, 2H), 4.20ppm (t, J = 6.2Hz, 2H), 4.13ppm (t, J = 6.2 Hz, 2H), 3.21-3.12ppm (m, 2H), 2.79-2.71ppm (m, 2H), 2.17-2.08ppm (m, 4H).
合成例13で得られた液晶配向剤D1 10.0gに対して合成例1で得られた重合性化合物RM1を0.06g(固形分に対して10質量%)添加し、室温で3時間攪拌して溶解させ、液晶配向剤D15を調製した。
得られた液晶配向剤D15を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Example 1>
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Synthesis Example 1 is added to 10.0 g of the liquid crystal aligning agent D1 obtained in Synthesis Example 13, and the mixture is stirred at room temperature for 3 hours. And dissolved to prepare liquid crystal aligning agent D15.
When the obtained liquid crystal aligning agent D15 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、重合性化合物RM1の量を、0.09g(固形分に対して15質量%)とした以外、実施例1と同様の方法により、液晶配向剤D16を調製した。
得られた液晶配向剤D16を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Example 2>
In Example 1, liquid crystal aligning agent D16 was prepared by the method similar to Example 1 except the quantity of polymeric compound RM1 having been 0.09g (15 mass% with respect to solid content).
When the obtained liquid crystal aligning agent D16 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、重合性化合物RM1の代わりに合成例2で得られた重合性化合物RM2を用いた以外、実施例1と同様の方法により、液晶配向剤D17を調製した。
得られた液晶配向剤D17を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Reference Example 1>
In Example 1, a liquid crystal aligning agent D17 was prepared in the same manner as in Example 1 except that the polymerizable compound RM2 obtained in Synthesis Example 2 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D17 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例2において、重合性化合物RM1の代わりに合成例2で得られた重合性化合物RM2を用いた以外、実施例2と同様の方法により、液晶配向剤D18を調製した。
得られた液晶配向剤D18を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Reference Example 2>
In Example 2, a liquid crystal aligning agent D18 was prepared in the same manner as in Example 2, except that the polymerizable compound RM2 obtained in Synthesis Example 2 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D18 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、重合性化合物RM1の代わりに合成例3で得られた重合性化合物RM3を用いた以外、実施例1と同様の方法により、液晶配向剤D19を調製した。
得られた液晶配向剤D19を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Reference Example 3>
In Example 1, a liquid crystal aligning agent D19 was prepared in the same manner as in Example 1 except that the polymerizable compound RM3 obtained in Synthesis Example 3 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D19 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例2において、重合性化合物RM1の代わりに合成例3で得られた重合性化合物RM3を用いた以外、実施例2と同様の方法により、液晶配向剤D20を調製した。
得られた液晶配向剤D20を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Reference Example 4>
In Example 2, a liquid crystal aligning agent D20 was prepared in the same manner as in Example 2, except that the polymerizable compound RM3 obtained in Synthesis Example 3 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D20 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、重合性化合物RM1の代わりに合成例4で得られた重合性化合物RM4を用いた以外、実施例1と同様の方法により、液晶配向剤D21を調製した。
得られた液晶配向剤D21を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Reference Example 5>
In Example 1, a liquid crystal aligning agent D21 was prepared in the same manner as in Example 1 except that the polymerizable compound RM4 obtained in Synthesis Example 4 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D21 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例2において、重合性化合物RM1の代わりに合成例4で得られた重合性化合物RM4を用いた以外、実施例2と同様の方法により、液晶配向剤D22を調製した。
得られた液晶配向剤D22を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Reference Example 6>
In Example 2, a liquid crystal aligning agent D22 was prepared in the same manner as in Example 2, except that the polymerizable compound RM4 obtained in Synthesis Example 4 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D22 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、液晶配向剤D1の代わりに合成例14で得られた液晶配向剤D2を用いた以外、実施例2と同様の方法により、液晶配向剤D23を調製した。
得られた液晶配向剤D23を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Example 3>
In Example 1, a liquid crystal aligning agent D23 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D2 obtained in Synthesis Example 14 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D23 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、液晶配向剤D1の代わりに合成例15で得られた液晶配向剤D3を用いた以外、実施例2と同様の方法により、液晶配向剤D24を調製した。
得られた液晶配向剤D24を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Example 4>
In Example 1, a liquid crystal aligning agent D24 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D3 obtained in Synthesis Example 15 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D24 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、液晶配向剤D1の代わりに合成例16で得られた液晶配向剤D4を用いた以外、実施例2と同様の方法により、液晶配向剤D25を調製した。
得られた液晶配向剤D25を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Example 5>
In Example 1, a liquid crystal aligning agent D25 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D4 obtained in Synthesis Example 16 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D25 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、液晶配向剤D1の代わりに合成例17で得られた液晶配向剤D5を用いた以外、実施例2と同様の方法により、液晶配向剤D26を調製した。
得られた液晶配向剤D26を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Example 6>
In Example 1, a liquid crystal aligning agent D26 was prepared in the same manner as in Example 2, except that the liquid crystal aligning agent D5 obtained in Synthesis Example 17 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D26 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、液晶配向剤D1の代わりに合成例18で得られた液晶配向剤D6を用いた以外、実施例2と同様の方法により、液晶配向剤D27を調製した。
得られた液晶配向剤D27を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Example 7>
In Example 1, a liquid crystal aligning agent D27 was prepared in the same manner as in Example 2, except that the liquid crystal aligning agent D6 obtained in Synthesis Example 18 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D27 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、液晶配向剤D1の代わりに合成例19で得られた液晶配向剤D7を用いた以外、実施例2と同様の方法により、液晶配向剤D28を調製した。
得られた液晶配向剤D28を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Example 8>
In Example 1, a liquid crystal aligning agent D28 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D7 obtained in Synthesis Example 19 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D28 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、液晶配向剤D1の代わりに合成例22で得られた液晶配向剤D10を用いた以外、実施例2と同様の方法により、液晶配向剤D29を調製した。
得られた液晶配向剤D29を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Example 9>
In Example 1, a liquid crystal aligning agent D29 was prepared in the same manner as in Example 2, except that the liquid crystal aligning agent D10 obtained in Synthesis Example 22 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D29 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、液晶配向剤D1の代わりに合成例24で得られた液晶配向剤D12を用いた以外、実施例2と同様の方法により、液晶配向剤D30を調製した。
得られた液晶配向剤D30を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Example 10>
In Example 1, a liquid crystal aligning agent D30 was prepared in the same manner as in Example 2, except that the liquid crystal aligning agent D12 obtained in Synthesis Example 24 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D30 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、液晶配向剤D1の代わりに合成例25で得られた液晶配向剤D13を用いた以外、実施例2と同様の方法により、液晶配向剤D31を調製した。
得られた液晶配向剤D31を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Example 11>
In Example 1, a liquid crystal aligning agent D31 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D13 obtained in Synthesis Example 25 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D31 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、液晶配向剤D1の代わりに合成例26で得られた液晶配向剤D14を用いた以外、実施例2と同様の方法により、液晶配向剤D32を調製した。
得られた液晶配向剤D32を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Example 12>
In Example 1, a liquid crystal aligning agent D32 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D14 obtained in Synthesis Example 26 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D32 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、重合性化合物RM1の代わりに合成例7で得られた重合性化合物RM7を用いた以外、実施例1と同様の方法により、液晶配向剤D33を調製した。
得られた液晶配向剤D33を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Example 13>
In Example 1, a liquid crystal aligning agent D33 was prepared in the same manner as in Example 1 except that the polymerizable compound RM7 obtained in Synthesis Example 7 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D33 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、重合性化合物RM1の代わりに合成例8で得られた重合性化合物RM8を用いた以外、実施例1と同様の方法により、液晶配向剤D34を調製した。
得られた液晶配向剤D34を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Example 14>
In Example 1, a liquid crystal aligning agent D34 was prepared in the same manner as in Example 1 except that the polymerizable compound RM8 obtained in Synthesis Example 8 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D34 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、重合性化合物RM1の代わりに合成例5で得られた重合性化合物RM5を用いた以外、実施例1と同様の方法により、液晶配向剤D35を調製した。
得られた液晶配向剤D35を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Comparative Example 1>
In Example 1, a liquid crystal aligning agent D35 was prepared in the same manner as in Example 1 except that the polymerizable compound RM5 obtained in Synthesis Example 5 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D35 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例2において、重合性化合物RM1の代わりに合成例5で得られた重合性化合物RM5を用いた以外、実施例2と同様の方法により、液晶配向剤D36を調製した。
得られた液晶配向剤D36を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物が確認された。 <Comparative example 2>
In Example 2, a liquid crystal aligning agent D36 was prepared in the same manner as in Example 2 except that the polymerizable compound RM5 obtained in Synthesis Example 5 was used instead of the polymerizable compound RM1.
The obtained liquid crystal aligning agent D36 was stored in a freezer at −20 ° C. for 1 day, and left to stand at room temperature for 3 hours to thaw, and precipitates were confirmed.
実施例1において、重合性化合物RM1の代わりに合成例6で得られた重合性化合物RM6を用いた以外、実施例1と同様の方法により、液晶配向剤D37を調製した。
得られた液晶配向剤D37を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物が確認された。 <Comparative Example 3>
In Example 1, a liquid crystal aligning agent D37 was prepared in the same manner as in Example 1 except that the polymerizable compound RM6 obtained in Synthesis Example 6 was used instead of the polymerizable compound RM1.
The obtained liquid crystal aligning agent D37 was stored in a freezer at −20 ° C. for 1 day, and allowed to stand at room temperature for 3 hours to thaw, and precipitates were confirmed.
実施例2において、重合性化合物RM1の代わりに合成例6で得られた重合性化合物RM6を用いた以外、実施例2と同様の方法により、液晶配向剤D38を調製した。
得られた液晶配向剤D38を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物が確認された。 <Comparative example 4>
In Example 2, a liquid crystal aligning agent D38 was prepared in the same manner as in Example 2, except that the polymerizable compound RM6 obtained in Synthesis Example 6 was used instead of the polymerizable compound RM1.
The obtained liquid crystal aligning agent D38 was stored in a freezer at −20 ° C. for 1 day, and allowed to stand at room temperature for 3 hours to thaw, and precipitates were confirmed.
実施例1において、重合性化合物RM1の代わりに合成例9で得られた重合性化合物RM9を用いた以外、実施例1と同様の方法により、液晶配向剤D39を調製した。
得られた液晶配向剤D39を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Comparative Example 5>
In Example 1, a liquid crystal aligning agent D39 was prepared in the same manner as in Example 1 except that the polymerizable compound RM9 obtained in Synthesis Example 9 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D39 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
実施例1において、重合性化合物RM1の代わりに合成例10で得られた重合性化合物RM10を用いた以外、実施例1と同様の方法により、液晶配向剤D40を調製した。
得られた液晶配向剤D40を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。 <Comparative Example 6>
In Example 1, a liquid crystal aligning agent D40 was prepared in the same manner as in Example 1 except that the polymerizable compound RM10 obtained in Synthesis Example 10 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D40 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
<液晶セルの作製>
実施例1で得られた液晶配向剤D15を用いて下記に示すような手順でSC-PVA方式の液晶セルの作製を行った。
実施例1で得られた液晶配向剤D15を、画素サイズが100μm×300μmでライン/スペースがそれぞれ5μmのITO電極パターンが形成されているITO電極基板のITO面にスピンコートし、80℃のホットプレートで90秒間乾燥した後、200℃の熱風循環式オーブンで30分間焼成を行い、膜厚100nmの液晶配向膜を形成した。
また、液晶配向剤D1を電極パターンが形成されていないITO面にスピンコートし、80℃のホットプレートで90秒乾燥させた後、200℃の熱風循環式オーブンで30分間焼成を行い、膜厚100nmの液晶配向膜を形成した。
上記の2枚の基板について一方の基板の液晶配向膜上に4μmのビーズスペーサーを散布した後、その上からシール剤(溶剤型熱硬化タイプのエポキシ樹脂)を印刷した。次いで、もう一方の基板の液晶配向膜が形成された側の面を内側にして、先の基板と貼り合せた後、シール剤を硬化させて空セルを作製した。この空セルに液晶MLC-6608(メルク社製商品名)を減圧注入法によって注入し、液晶セルを作製した。作製した液晶セルは、その後、120度の熱風循環式オーブンに1時間入れ、液晶の再配向処理を行った。
得られた液晶セルの応答速度を、下記方法により測定した。その後、この液晶セルに15VのDC電圧を印加した状態で、この液晶セルの外側から365nmのバンドパスフィルターを通したUVを10J/cm2照射した。その後、再び応答速度を測定し、UV照射前後での応答速度を比較した。また、UV照射後のセルについて画素部分のプレチルト角を測定した。また、UVを照射していないセルを一日放置し、その後、液晶セルの偏光顕微鏡観察を行った。重合性化合物の溶解性が低い場合、液晶セル中でも析出しやすくなり、輝点が発生すると考えられる。結果を表5に示す。 <Example 15>
<Production of liquid crystal cell>
Using the liquid crystal aligning agent D15 obtained in Example 1, an SC-PVA liquid crystal cell was prepared according to the following procedure.
The liquid crystal aligning agent D15 obtained in Example 1 was spin-coated on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm was formed, and then heated at 80 ° C. After drying on a plate for 90 seconds, baking was performed in a hot air circulation oven at 200 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.
Further, after spin-coating the liquid crystal aligning agent D1 on the ITO surface on which the electrode pattern is not formed and drying for 90 seconds on a hot plate at 80 ° C., baking is performed for 30 minutes in a hot air circulation oven at 200 ° C. A 100 nm liquid crystal alignment film was formed.
After spraying 4 μm bead spacers on the liquid crystal alignment film of one of the two substrates, a sealant (solvent type thermosetting epoxy resin) was printed thereon. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing agent was cured to produce an empty cell. Liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to produce a liquid crystal cell. The prepared liquid crystal cell was then placed in a 120 ° hot air circulation oven for 1 hour to realign the liquid crystal.
The response speed of the obtained liquid crystal cell was measured by the following method. Thereafter, with a DC voltage of 15 V applied to the liquid crystal cell, UV was applied from the outside of the liquid crystal cell through a 365 nm bandpass filter at 10 J / cm 2 . Thereafter, the response speed was measured again, and the response speed before and after UV irradiation was compared. Further, the pretilt angle of the pixel portion of the cell after UV irradiation was measured. In addition, a cell that had not been irradiated with UV was left for one day, and then the liquid crystal cell was observed with a polarizing microscope. When the solubility of the polymerizable compound is low, it is likely to be precipitated even in the liquid crystal cell and a bright spot is generated. The results are shown in Table 5.
まず、バックライト、クロスニコルの状態にした一組の偏光板、光量検出器の順で構成される測定装置において、一組の偏光板の間に液晶セルを配置した。このときライン/スペースが形成されているITO電極のパターンがクロスニコルに対して45°の角度になるようにした。そして、上記の液晶セルに電圧±6V、周波数1kHzの矩形波を印加し、光量検出器によって観測される輝度が飽和するまでの変化をオシロスコープにて取り込み、電圧を印加していない時の輝度を0%、±4Vの電圧を印加し、飽和した輝度の値を100%として、輝度が10%から90%まで変化するのにかかる時間を応答速度とした。 <Measurement method of response speed>
First, a liquid crystal cell was arranged between a pair of polarizing plates in a measuring apparatus configured in the order of a backlight, a pair of polarizing plates in a crossed Nicol state, and a light amount detector. At this time, the ITO electrode pattern in which the line / space was formed was at an angle of 45 ° with respect to the crossed Nicols. Then, a rectangular wave with a voltage of ± 6 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the change until the luminance observed by the light quantity detector is saturated is captured by an oscilloscope. The luminance when no voltage is applied is obtained. A voltage of 0% and ± 4 V was applied, the saturated luminance value was set to 100%, and the time taken for the luminance to change from 10% to 90% was defined as the response speed.
名菱テクニカ製LCDアナライザーLCA-LUV42Aを使用した。
<実施例16~実施例28>
液晶配向剤D15の代わりに、表1記載の液晶配向剤を用いた以外は実施例21と同様の操作を行って、UV照射前後での応答速度を比較した。またプレチルト角の測定を行った。また、液晶セル中の輝点観察結果も行った。 <Measurement of pretilt angle>
An LCD analyzer LCA-LUV42A manufactured by Meiryo Technica was used.
<Example 16 to Example 28>
Instead of the liquid crystal aligning agent D15, the same operation as in Example 21 was performed except that the liquid crystal aligning agent described in Table 1 was used, and the response speed before and after UV irradiation was compared. The pretilt angle was measured. Moreover, the bright spot observation result in a liquid crystal cell was also performed.
合成例22で得られた液晶配向剤D10(10.0g)に、合成例27で合成したRM13を0.06g(液晶配向剤D10)の固形分に対して10質量%)添加し、室温で3時間撹拌して溶解させ、液晶配向剤D41を調製した。
得られた液晶配向剤D41を-20℃の冷凍庫で1日保存し、室温で3時間放置し解凍したところ、析出物は確認されなかった。
<実施例30>
実施例29で調製した液晶配向剤D41を実施例15と同様の操作を行い、UV照射前後での応答速度を比較した。またプレチルト角の測定と液晶セル中の輝点観察を行った。 <Example 29>
To the liquid crystal aligning agent D10 (10.0 g) obtained in Synthesis Example 22, RM13 synthesized in Synthesis Example 27 was added at 0.06 g (10% by mass with respect to the solid content of the liquid crystal aligning agent D10)) at room temperature. The liquid crystal aligning agent D41 was prepared by stirring and dissolving for 3 hours.
When the obtained liquid crystal aligning agent D41 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.
<Example 30>
The liquid crystal aligning agent D41 prepared in Example 29 was subjected to the same operation as in Example 15, and the response speed before and after UV irradiation was compared. The pretilt angle was measured and the bright spot in the liquid crystal cell was observed.
液晶配向剤D15の代わりに、それぞれ液晶配向剤D17~D22を用いた以外は実施例16と同様の操作を行って、UV照射前後での応答速度を比較した。またプレチルト角の測定を行った。また、液晶セル中の輝点観察結果も行った。
なお、参考例7,8,11,12では、200℃の熱風循環式オーブンの代わりに140℃の熱風循環式オーブンを使用した。 <Reference Example 7 to Reference Example 12>
The response speed before and after UV irradiation was compared by performing the same operation as in Example 16 except that the liquid crystal aligning agents D17 to D22 were used instead of the liquid crystal aligning agent D15. The pretilt angle was measured. Moreover, the bright spot observation result in a liquid crystal cell was also performed.
In Reference Examples 7, 8, 11, and 12, a 140 ° C. hot air circulation oven was used instead of the 200 ° C. hot air circulation oven.
液晶配向剤D15の代わりに、それぞれ液晶配向剤D35~D40を用いた以外は実施例15と同様の操作を行って、UV照射前後での応答速度を比較した。またプレチルト角の測定を行った。また、液晶セル中の輝点観察結果も行った。 <Comparative Examples 7 to 12>
The response speeds before and after UV irradiation were compared by performing the same operation as in Example 15 except that the liquid crystal aligning agents D35 to D40 were used instead of the liquid crystal aligning agent D15. The pretilt angle was measured. Moreover, the bright spot observation result in a liquid crystal cell was also performed.
同様な観点で、実施例27と、比較例11(RM7とRM9とは、F置換の有り(RM7)・なし(RM9)の違い)、実施例28と比較例12(RM8とRM10とは、F置換の有り(RM8)・なし(RM10)の違い)を比較すると、液晶への溶解性が向上していることがわかる。また、参考例9及び参考例10から、ビフェニル骨格よりも剛直で溶解性の低いターフェニル骨格を有していても、ハロゲン基の導入で重合性化合物の溶解性が向上し、液晶配向剤の保存安定性も向上することが確認できる。
同様に、参考例7、8、11、12からも、重合性化合物の高い溶解性が確認された。よって、ハロゲン置換された重合性化合物は、重合性化合物の溶解性が向上し、液晶配向剤が高い保存安定性を示し、さらに、液晶への溶解性も向上することがわかる。また、ハロゲン置換された重合成化合物を添加した液晶配向剤は、SC-PVA方式の液晶セルにおいて、ハロゲン置換されていない重合性化合物を添加した液晶配向剤と同様にチルト角を発現することが確認された。 When Examples 15 and 16 are compared with Comparative Examples 7 and 8, particularly when Example 16 and Comparative Example 8 are compared, when the same skeleton is present (RM1 and RM5 have F substitution (RM1) / none (Difference in (RM5)), it can be seen that the introduction of a halogen group improves the solubility in varnish. In addition, it is understood that the solubility in the liquid crystal is also improved by observation of the bright spot in the liquid crystal cell.
From the same viewpoint, Example 27 and Comparative Example 11 (RM7 and RM9 are different in F substitution (RM7) / No (RM9)), Example 28 and Comparative Example 12 (RM8 and RM10 are Comparing the presence of F substitution (RM8) and absence (RM10)), it can be seen that the solubility in liquid crystal is improved. Further, from Reference Example 9 and Reference Example 10, even when the terphenyl skeleton is rigid and less soluble than the biphenyl skeleton, the introduction of the halogen group improves the solubility of the polymerizable compound, and the liquid crystal aligning agent It can be confirmed that the storage stability is also improved.
Similarly, from Reference Examples 7, 8, 11, and 12, high solubility of the polymerizable compound was confirmed. Therefore, it can be seen that the halogen-substituted polymerizable compound improves the solubility of the polymerizable compound, the liquid crystal aligning agent exhibits high storage stability, and further improves the solubility in the liquid crystal. In addition, a liquid crystal aligning agent to which a halogen-substituted polysynthetic compound is added can exhibit a tilt angle in a SC-PVA liquid crystal cell in the same manner as a liquid crystal aligning agent to which a non-halogen-substituted polymerizable compound is added. confirmed.
Claims (8)
- ハロゲン原子で少なくとも一置換されているアリール基と、2個のα-メチレン-γ-ブチロラクトン基を有する重合性化合物。 A polymerizable compound having an aryl group at least monosubstituted with a halogen atom and two α-methylene-γ-butyrolactone groups.
- 下記の式[1]で表されることを特徴とする重合性化合物。
- 式[1]中、Arは下記式[2]乃至[4]で表される構造からなる重合性化合物。(Xはハロゲン置換基を示し、m1~m6は各々独立に0~4の整数であり、m7およびm8は各々独立に0~3の整数であり、m1+m2は1以上8以下であり、m3+m4+m5は1以上12以下であり、m6+m7+m8は1以上10以下である)
- Xがフッ素基を示す請求項1~3のいずれか一項に記載の重合性化合物。 The polymerizable compound according to any one of claims 1 to 3, wherein X represents a fluorine group.
- 式[2]乃至[4]中、Xはフッ素基を示し、m1+m2は1以上3以下であり、m3+m4+m5は1以上4以下であり、m6+m7+m8は1以上3以下である請求項4記載の化合物。 In formulas [2] to [4], X represents a fluorine group, m 1 + m 2 is 1 or more and 3 or less, m 3 + m 4 + m 5 is 1 or more and 4 or less, and m 6 + m 7 + m 8 is The compound according to claim 4, which is 1 or more and 3 or less.
- 請求項1~7のいずれか1項に記載の重合性化合物と、ポリイミド及びポリイミド前駆体から選ばれる少なくとも一種の重合体とを含有する液晶配向剤。 A liquid crystal aligning agent comprising the polymerizable compound according to any one of claims 1 to 7 and at least one polymer selected from polyimide and a polyimide precursor.
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